Optical element

ABSTRACT

An optical element in which a hard coat layer is formed on an organic glass base material surface via a primer layer. For a primer composition forming a primer layer, whole or the main body of the primer layer formation polymer is made as being ester based TPE. Moreover, a hard coat composition forming a hard coat layer is consisted of a hydrolysate of alkoxysilane in which trialkoxysilane containing monoexpoxy organic group is the main body as a matrix formation ingredient, and the titanium based metal oxide complex particle as being an optical interference control agent, the foregoing titanium based metal oxide complex particle is consisted of T 1 O 2  as the main body, SiO 2  as a major sub-ingredient, and further, ZrO 2  and K 2 O as a trace sub-ingredient. An optical element of the present invention is capable of suppressing optical interference even if it is a high refractive index base material and the stability of coated film portion is also excellent as well as has a variety of properties comparable to the conventional optical parts.

TECHNICAL FIELD

The present invention relates to an optical element. More particularly,the present invention relates to a hard coat composition, a primercomposition in the surface of the optical element, a surface processingtechnology such as a reflection prevention film and the like and adyeing method. The present invention is preferable for an optical part(optical element) of an organic glass base material having particularlya high refractive index.

As used herein, the term “optical element” refers to a concept whichincludes, but not limited to, original optical elements such as a lensfor glasses, a lens for camera, a lens for microscope, a lens fortelescope, a lens for binocular, a reflecting mirror, a prism and thelike, also includes a filter, a cover for a lighting fitting and thelike.

In the following description, a lens for glasses (optical lens) will bemainly exemplified and described, but not limited to this.

BACKGROUND ART

In recent years, as a material of an optical lens, an organic glass hasbeen popular among the people, which is lightly weighted, and excellentat shock resistance, having chromatophilia and easily processedcomparing with an inorganic glass. Among these, an organic glass havinga high refractive index, which is capable of thinning the thickness oflens (refractive index, around 1.60) has been widely used. However, ingeneral, an organic glass has a lower abrasive resistance (resistanceagainst scraping and damaging) compared with an inorganic glass,therefore, easily scraped and damaged. Hence, in general, a hard coat(silicone-based hardening film coating) is performed on the surface ofthe organic glass base material (hereinafter, it may be referred to onlyas “base material”). Furthermore, in a lens for glasses, from thereasons such as the esthetic reason and the like, an inorganicreflection prevention film is often formed by dry plating such as vapordeposition and the like of inorganic substances.

However, as described above, a lens to which both a hard coat and aninorganic reflection prevention film have been provided had anon-conformity of shock resistance being inferior. Hence, in order toenhance the shock resistance, a variety of technical concepts in whichbetween the base material and the hard coat, a primer layer consisted ofpolyurethane based coating (mainly, urethane base thermoplasticelastomer (hereinafter, referred to as “TPU”) is made coating filmformation element) is intervened have been proposed.

Then, it is necessary to secure the refractive index similar to the basematerial in each layer in order to prevent the optical interference of alens in the case where the above-described hard coat layer and primerlayer are laminated on a base material having a high refractive index.

The present inventors have previously proposed a primer compositionwhich prevents the occurrence of optical interference even if the basematerial has relatively a high refractive index (see Japanese UnexaminedPatent Publication No. Hei 6-82694) and a hard coat composition having ahigh refractive index (see Japanese Patent No. 2577670), and one portionof these has been developed to put to practical use.

However, as a trend in recent years, the fashionability has beenconsidered as a more important factor, as the needs which the thicknessof lens edge face has to be thinner are enhanced, a super highrefractive organic lens having a higher refractive index (refractiveindex 1.70) has been commercially available in the optical industry.

Then, it has been found that it is difficult to suppress the lightinterference in the case where a hard coat composition described in theabove-described Japanese Patent No. 2577670 is coated on theabove-described lens having a super high refractive index.

Moreover, it has been found that after the long term of usage of lenshas been passed, the hard coat layer causes the blackening phenomenondue to the ultraviolet ray to occur and esthetic aspect is damaged. Thisblackening phenomenon is estimated on the basis of iron oxide in theiron oxide/titanium oxide complex oxide particle which has been used asa hard coat ingredient.

Furthermore, it has been found that the primer composition described inthe above-described Japanese Unexamined Patent Publication No. Hei6-82694 lowers the heat resistance of the base material, and thematerial is easily non-uniform within the layer, therefore, cloudinessdue to the irregular reflection of light is recognized.

On the other hand, the above-described material having a high refractiveindex is more difficult to dye comparing with a material having a lowerrefractive index. Therefore, in the immersion dyeing method in which thebase material is immersed in an aqueous dye bath (aqueous solution)which uses disperse dye and the like, the problems listed below havebeen easily occurred.

It is difficult for an immersion dyeing method to perform a dyeing of auniform and stable coloring to the base material. This is the reason whythe dyeing property (dyeing speed and dyeing equilibrium) is easilyinfluenced with the respective ingredient concentration of dye aqueousdispersion liquid (disperse dye, surfactant, dyeing promoter and thelike) and variation of dyeing temperature, and further, the kind of anorganic glass base material. Moreover, in the case where a higherconcentration dyeing (dyeing property) is required, it needs to dye fora long time period. Moreover, since it is the dyeing in the lowtemperature and the dyeing property is not sufficient, fading in thecoloring in the subsequent steps is significant, it is difficult tofinish it in the desired coloring.

In order to solve the problem of the above-described immersion dyeingmethod, for example, a method of heating and transcribing the dye(migration) after the dye is sublimed at gaseous phase and the dyeinglayer is formed on the surface of the glass surface (Japanese UnexaminedPatent Publication No. Sho 56-159376 and the like), and a method ofadhering the transcribed film which has been dyed on the surface of anorganic glass base material and heating and transcribing (JapaneseUnexamined Patent Publication No. 2000-17586 and the like) have beenproposed.

However, in the former method, since the sublimation temperatures aredifferent depending on the dyes, it is difficult to obtain the desiredcoloring, coloring concentration on and in the base material, and in thelatter method, it is difficult to precisely adhere the transcriptionfilm on the curved surface and it is difficult to obtain a uniformwithout coloring variation on and in the base material.

The first object of the present invention is to provide a primercomposition in which refractive index can be adjustable without loweringthe heat resistance of the base material and the cloudiness due to theirregular reflection of light is slight as well as the similarcharacteristics (shock resistance, scraping and damaging resistance andthe like) as the conventional primer composition can be conferred and anoptic element utilizing the primer composition.

The second object of the present invention is to provide a hard coatcomposition which is capable of suppressing the optical interferencewith respect to a base material having a super high refractive index andis excellent at light resistance without damaging the esthetic aspecteven if the optic part is used for a long term without occurring theblackening phenomenon due to the ultraviolet and an optical elementutilizing the hard coat composition.

The third object of the present invention is to provide an organic glassoptic element in which the adhesion with the hard coat layer, thescraping and damaging resistance and the heat resistance are excellentin an optic element having the above-described hard coat layer, and theforegoing organic glass optic element having a reflection preventionfilm having an excellent reflection prevention effect in the wide rangeof wavelengths and the foregoing reflection prevention film capable ofbeing well colored in an interference color of green which is generallyrequired for lens for glasses.

The fourth object of the present invention is to provide a compositionfor dyeing an organic glass capable of stably and well dyeing andfurther dyeing it to the required coloring and a method of dyeing anorganic glass.

DISCLOSURE OF THE INVENTION

(1) The first invention achieves the above-described first object with aprimer composition of the following constitution and a primer elementconsisted of the relevant primer composition.

A primer composition of the present invention is characterized in thatit is a composition for forming a primer layer between an organic glassand a silicone based hardening coating film, and whole of or the mainbody of the primer layer forming polymer is a polyester basedthermoplastic elastomer (ester based TPE).

It is desirable that the above-described primer composition contains ametal oxide particle as an optical interference control agent(refractive index preparation).

It is desirable that the above-described ester based TPE molar ratio ofthe hard segment and the soft segment is the former/thelatter=30/70-90/10, and the relevant ester base TPE exhibits thecharacteristics of surfacial hardness (shore hardness D): 35-75 and bendelasticity: 40-800 MPa.

(2) The second invention achieves the above-described second object byan optic element having a hard coat layer consisted of a hard coatcomposition of the following constitution and the relevant hard coatcomposition.

A hard coat composition of the present invention is characterized inthat hydrolysate of alkoxysilane consisted of trialkoxysilane as themain body containing monoepoxy organic group is made a matrix formationingredient, and titania based metal oxide complex particle is made opticinterference control agent (refractive index preparation), the titaniabased metal oxide complex particle is made consisted of TiO₂ as the mainbody, SiO₂ as the major sub-ingredient, and further, ZrO₂ and K₂O as atrace sub-ingredient.

For the above-described titania based metal oxide complex particle, itis desirable that its average particle diameter is made as 1-50 nm, itscomposition is made as satisfying the respective weight ratio ofSiO₂/TiO₂=0.1900-0.2100, ZrO₂/TiO₂=0.0015-0.023, K₂O/TiO₂=0.0012-0.012,and the contents are made as 40-100 weight portions with respect to thetotal alkoxysilane 100 weight portions.

Moreover, it is desirable that trialkoxysilane containing monoepoxyorganic group is consisted of one or more species selected from thegroup expressed by the following general formula (1):

General Formula (1)

(where R¹ represents H or CH₃, R² represents alkylene group having thenumber of carbon atoms of 1-4. R³ represents alkyl group having thenumber of carbon atoms of 1-4), or, from the group expressed by thefollowing general formula (2):

General Formula (2)

(where R¹ represents alkylene group having the number of carbon atoms of1-4 and R² represents alkyl group having the number of carbon atoms of1-4)

Furthermore, it is desirable that as alkoxysilane except for theforegoing trialkoxysilane containing monoepoxy organic group,tetraalkoxysilane indicated by the following general formula (3):

 Si (OR¹)₄  

General Formula (3)

is used, and the content of the tetraalkoxysilane is made less than 20wt % in the total alkoxysilane.

Moreover, it is desirable that it contains an organic metal compound asa hardening agent of the matrix formation ingredient, the relevantorganic metal compound(s) of one or more species selected from the groupof chelating compounds of Cr (III), Co (III), Fe (III), Zn (II), In(III), Zr (IV), Y (III), Sn, V, Al (III), Ti (II) with which a chelatingagent selected from ethylenediamine-tetraacetic acid (EDTA),hexafluoroacetylacetone, trifluoroacetylacetone, acetyl acetone andmethyl acetoacetate coordinates are used.

An organic glass base material to which a hard coat composition of thesecond invention is applied is preferably indicates 1.66 or more of therefractive index.

As an organic glass indicating more than 1.66 of the above-describedrefractive index, an organic glass obtained by polymerizing and reacting(1) active hydrogen compounds of one or more species selected from thegroup of polyol, polythiol and hydroxy compound having a mercapto group,and (2) one or more species selected from the group ofpolyisothiocyanate compound or isothiocyanate compound having anisocyanate group, or, an organic glass obtained by polymerizing andreacting episulfide compound having more than two pieces of structuresindicated by the following general formula (4)and a ring-like frame:

General Formula (4)

(where X represents S or O, and the number of pieces of S is more than50% on average with respect to the total of S and O constitutingthree-membered ring)

(3) The third invention achieves the above-described object by furtherlaminating a reflection prevention film layer of an inorganic substancebased one of the following constitution on the above-described hard coatlayer.

The configuration of the reflection prevention film is characterized inthat as design center wavelength λ is made as in the range of 450-550nm, from the foregoing hard coat layer side, it has a multiple layersstructure in which a medium refractive index layer having 0.19-0.29 λ ofan optic film thickness, a high refractive index layer having 0.42-0.58λ of an optic film thickness and a low refractive index layer having0.19-0.29 λ of an optic film thickness were in turn formed.

Furthermore, it is desirable that the medium refractive index layer andthe high refractive index layer are consisted of equivalent layer usingmore than two layers whose refractive index are different, respectively.

It is desirable that in a method of forming the above-describedreflection prevention film, before the formation of the reflectionprevention film, the cleaning processingof the surface of the hardcoatlayer is performed by an ion irradiation.

Then, it is desirable that among the reflection prevention films, theformation of at least high refractive index layer is performed by an ionbeam assist method using vapor deposition technique.

(4) A composition for dyeing an organic glass and a method of dyeing anorganic glass of the fourth invention achieves the foregoing fourthobject.

A composition f or dyeing an organic glass of the fourth invention ischaracterized in that the dye is made as insoluble-in- water dye, dyecarrier agent (sizing agent) is made as acryl based resin, the dyedissolving agent is made as an organic solvent in the range of 8-11 ofSP value.

Then, it is desirable that the blending weight ratio of acryl basedresin and insoluble-in-water dye is made as the former/thelatter=60/40-5/95.

The above-described method of dyeing is characterized in that migrationis performed to the base material to be dyed by attaching theabove-described composition for dyeing on an organic glass base materialor an organic glass base material equipped with a hard coat layer(hereinaf ter, referred to as “base material to be dyed”) and bysublimating non-aqueous dye.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical representation showing the relationship betweenwavelength and reflectivity of lens prepared in Example 4 in theexperimental example.

FIG. 2 is a graphical representation showing the relationship betweenwavelength and reflectivity of lens prepared in comparative Example 4.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, each constitution of the present invention will bedescribed below in detail. Hereinafter, a blending unit will beconsidered as a weight unit unless there is particular notice thereof.

A. It is presumed as the prerequisite requirement that a primercomposition of the present invention is provided for forming a primerlayer between an organic glass and a silicone based hardening coatingfilm.

(1) As the above-described organic glass, there is no particularlimitations if its refractive index is in the range from 1.40 to 1.75,and polymethylmetacrylate, fatty polyallylcarbonate, aromaticpolyallylcarbonate, polysulfone, polythiourethane (thiourethane resin),polythioepoxy (thioepoxy resin) and the like can be listed. Among these,aromatic polyallylcarbonate, polysulfone, polythiourethane,polythioepoxy, which easily achieve a high refractive index (1.66 ormore) are desirable.

(2) As for the above-described silicone based hardening coating film(hard coat film), there is no limitations if it is a silicone based one.

For example, catalyst, metal oxide particle (including complex particle)are added to the hydrolysate of organoalkoxy silane, and its viscosityis adjusted by diluent solvent so as to be capable of being coated.Furthermore, the addition of a surfactant, a ultraviolet absorbent andthe like can be also performed to this hard coat liquid.

(i) As the above-described organoalkoxysilane, these indicated by thefollowing general formula is capable of being used:

R ¹ _(a) R ² _(b) Si (OR ³)₄−(a+b)

(where R¹ represents alkyl group, vinyl group, epoxy group, methacryloxygroup, and phenyl group, each having the number of carbon atoms of 1-6,R² represents alkyl group, alkylene group, cycloalkyl group, alkylhalide group, aryl group, arylalkyl group, and alkylaryl group, eachhaving the number of carbon atoms of 1-3, and R³ represents alkyl group,alkylene group, cycloalkyl group, alkoxyalkyl group, and arylalkylgroup, each having the number of carbon atoms of 1-4. Moreover, a=0 or1, b=0, 1 or 2.) Concretely, tetramethoxysilane, methyltrimethoxysilane,vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane,trimethylchlorosilane, glycidoxymethyltrimethoxysilane,α-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltrimethoxysilane,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilaneand the like can be listed. Other than that these can be used singly,two kinds or more of these can be also used in combination.

(ii) As the above-described catalyst, organic carboxylic acid such astrimellitic acid, trimellitic anhydride, itaconic acid, pyromelliticacid, pyromellitic anhydride and the like, organic compound containingnitrogen such as methyllmidazole dicyandiamide and the like, metalalkoxide such as titanium alkoxide, zirconium alkoxide and the like,metal complex such as aluminum acetylacetone, iron (III) acetylacetoneand the like, alkaline metal organic carboxylate such as sodium acetate,potassium acetate and the like can be used.

(iii) As a metal oxide particle, colloidal silica, colloidal titania,colloidal zirconia, colloidal cerium (IV) oxide, colloidal tantalum (V)oxide, colloidal tin (IV) oxide, colloidal antimony (III) oxide,colloidal alumina, colloidal iron (III) oxide and the like, which havemean particle diameter of 5˜50 im, can be used, and other than thatthese can be used singly, two kinds or more of these can be also used incombination, or these can be also used as a complex particle.

(iv) As a diluent solvent, polar solvent such as alcohols, ketones,esters, ethers, Cellosolves and the like can be preferably used.

(v) As a method of coating, it is selected from the known methods suchas dipping method, spin coat method and the like. A hardening conditionsare made as being at 80-130° C. for 1-4 hours.

(3) Usually, a reflection prevention film is formed on theabove-described silicone based hardening coating film. The formation ofthe relevant reflection prevention film is usually performed bydry-plating method such as vacuum vapor deposition, spattering, ionplating and the like using inorganic particle such as metal, metaloxide, metal fluoride.

As an inorganic substance for forming a reflection prevention film,metal oxide such as silica, titania (IV), tantalum (V) oxide, antimony(III) oxide, zirconia, alumina and the like, and metal fluoride such asmagnesium fluoride and the like can be preferably used.

B. A primer composition of the present invention is characterized inthat whole of or the main body of the primer layer formation polymer isester based TPE (hereinafter, referred to as “TPEE”), and it contains ametal oxide particle as optical interference control agent according tothe necessity.

(1) As a TPEE, both polyester-polyether type and polyester-polyestertype can be used.

The above-described TPEE is a multiblock copolymer in which polyester isused for the hard segment, polyether or polyester is used for the softsegment.

Then, the weight ratio of the hard segment and the soft segment of therelevant TPEE is made as the former/the latter=30/70-90/10, andpreferably, 40 /60-80/20. In the case where the ratio of the hardsegment is less than 30%, the hardness, modulus, mechanical strength andheat resistance are lowered, and in the case where the ration of thehard segment exceeds over the 90%, the rubber elasticity and theproperties at a lower temperature are lowered.

Then, it is desirable that ester based TPE indicates the surfacehardness (shore hardness D) in the range of 35-75, the bend elasticityin the range of 40-800 MPa.

Hereinafter, constitutional ingredients of the hard segment and softsegment of TPEE will be concretely exemplified.

(i) Polyester as a Hard Segment Constitutional Ingredient

Basically, these are consisted of dicarboxylic acids and small moleculeglycol.

As dicarboxylic acid, aromatic dicarboxylic acid such as terephthalicacid, isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acidand the like, linear saturated fatty dicarboxylic acid having the numberof carbon atoms of 4-20 such as succinic acid, adipic acid, azelaicacid, decamethylenedicarboxylic acid, octadecandicarboxylic acid and thelike, fatty oxocarboxylic acid (see the following general formula) suchas ε-oxycapronic acid and the like, dimeric acid (dibasic acid in whichfatty monocarboxylic acid having double bond is dimmericly polymerized)and the like, and ester formative derivatives of these are listed. Amongthese, terephtalic acid, 2, 6-naphthalenedicarboxylic acid arepreferable at the time of being used.

General formula R¹CO(CH₂)_(n)COOH

Note) R¹: alkyl group or H, n: 0-19.

As a small molecule glycol, fatty glycol such as ethylene glycol,trimethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol,neopentyl glycol and the like, fatty glycol such as 1,6-cyclohexanedimethanol and the like and ester formative derivatives ofthese are listed. Among these, ethylene glycol and 1, 4-butanediol arepreferable at the time of being used.

(ii) Polyester as Soft Segment Constitutional Ingredient

Consisted of dicarboxylic acids and long chain glycol, and as adicarboxylic acid the foregoing ones are listed.

As a long chain glycol, poly (1, 2-butadiene glycol), poly (1,4-butadiene glycol) and its hydrogen additives and the like are listed.

Moreover, ε-caprolactone (C6). enantholactone (C7) and caprylolactone(C8) are also useful as a polyester ingredient.

Among these, ε-caprolactone is preferable at the time of being used.

(iii) Polyether as Soft Segment Constitutional Ingredient

Poly (alkylene oxide) glycols such as poly (ethylene oxide) glycol, poly(1, 2-propylene oxide) glycol, poly (1, 3-propylene oxide) glycol, poly(tetramethylene oxide) glycol and the like are listed, among these, poly(tetramethylene oxide) glycol is desirable at the time of being used.

The above-described TPEE is capable of being manufactured by the methodof common use. Concretely, lower alkyl ester of dicarboxylic acid, fattylong chain glycol and excessive small molecule glycol are heated at thetemperature of 150-200° C. in the presence of catalyst such astetrabutyltitanate and the like, ester exchange is performed, first, lowpolymer is formed, and further, this low polymer is heated and agitatedunder the high vacuum at the temperature of 220-280° C.,polycondensation is performed to be TPEE. The foregoing low polymer canbe also obtained by performing the direct esterification reaction ofdicarboxylic acid, long chain glycol and small molecule glycol.

In the above-described description, as a polymer capable of beingcombined in the case where TPEE is not made to be whole of the coatingfilm formation polymer, but is made as its main body, there is nolimitations if it is capable of being mixed with TPEE, usual ester basedresins (PBT, PET and the like), amide based resin, and further, amidebased TPE and the like are optionally used, and usually, the ratiooccupying in polymer as a whole, is less than 50%, and desirably lessthan 30%.

These TPEE may be added in a form of solution-type, however, it isdesirable from the viewpoint of workability and the protection ofenvironment that it is added in a form of aqueous emulsion.

Although this aqueous emulsification can be performed by the method ofcommon use, concretely, a forced emulsification method in which apolymer is mechanically cut and forcefully emulsified in the presence ofsurfactant (external emulsion) is desirable.

As a surfactant usually used, (i) anionic surfactant;alkylbenzenesulfonic acid soda such as sodium laurylbenzenesulfonicacid, sodium dioctylsulfosuccinate and the like, (ii)cationicsurfactant; quaternary ammonium salt, (iii) nonionic surfactant:polyethylene glycol, ethylene oxide additives of long chain alcohol,ethylene oxide additives of alkylphenol and the like are listed, Amongthese, sodium laurylbenzenesulfonic acid is desirable at the time ofbeing used.

Moreover, an ionic hydrophilic group is introduced to a polymer, by anauto emulsification method in which it is stably dispersed into waterwithout any assistance of an emulsion or the methods may be used incombination.

It is desirable that the relevant primer composition (coating) is madeto contain metal oxide particle (including complex particle) for thepurpose of adjusting the refractive index and enhancing the strength andthe like.

For this metal oxide particle, one used for a hard coat described abovecan be used, it is desirable that from the viewpoint of the handling, itis added in a form of colloidal solution (sol) of the metal oxideparticle (colloidal particle). It is desirable that this colloidalsolution is appropriately used while its disperse medium is replacedwith a polar solvent used for the primer described later.

For example, colloidal silica, colloidal titania, colloidal zirconia,colloidal cerium (IV) oxide, colloidal tantalum (V) oxide, colloidal tin(IV) oxide, colloidal antimony (III) oxide, colloidal alumina, colloidaliron (III) oxide and the like, whose average particle diameter is in therange of 1-100 μm, desirably in the range of 5-50 μm can be used. Otherthan that these are capable of being used singly, two kinds or more ofthese can be also capable of being, used in combination, or these arealso capable of being used as a complex particle.

At this time, the blending ratio (weight) of the metal oxide particle ismade as the metal oxide particle/TPEE=1/99-80/20, desirably, 2/98-70/30,more desirably, 4/96-60/40. In the case where the metal particle is lessthan 1%, it is difficult to exert the refractive index adjustmentaction, and in the case where the metal particle exceeds over 80%, theshock resistance becomes inferior, and the cloudiness is significantlyemerged by the scattering of light.

(e) Then, as a primer composition of the present invention consisted ofthese respective ingredients, usually, one or more than two kinds of thepolar solvents similar to these used for the foregoing coating for thehard coat, that is, alcohols, ketones, esters, ethers, and Cellosolves(monoalkyl ether of ethylene glycol) and the like are used incombination while adding a diluent solvent.

Moreover, as to a primer composition of the present invention, theblending of the ultraviolet ray absorbent such as benzophenon based one,benzotriazole based one, and phenol based one and the like and theblending of a leveling agent containing a silicone based surfactant,fluorine based surfactant and the like for the purpose of enhancing thesmoothness of the coating and the blending of the other reforming agentare capable of being carried out.

As a coating method, a method is selected from the known methods such asa dipping method, a spin coat method and the like. The hardening of theprimer layer comprises the preliminary hardening and the main hardening.The conditions of the preliminary hardening are made as being roomtemperature up to 150° C. for 3 minutes to 2 hours, and desirably in therange from 80 to 110° C. for 5 minutes to 1 hour. Since the mainhardening is performed at the same time with the silicone based hardcoat, the conditions is the hardening conditions of the afore-describedhard coat (80-130° C.×1-4 hours). In the case where the preliminaryhardening is exceeded over a long time at a high temperature, theadhesiveness with upper layer silicone based hard coat film is lowered,and in the case where the preliminary hardening is not sufficient, thecoating film is likely to be milkiness.

The film thickness of this primer layer is made as being in the range of0.01-10 μm, and desirably in the range of 0.1-10 μm. In the case whereit is less than 0.01 μm, the effect of the shock resistance is notexpected to be enhanced, and in the case where it exceeds over 10 μm, aproblem involving with the surface precision becomes easily occurred.

As the other reforming agent, poly (vinyl butyral) can be used as athickener for enhancing the film thickness without lowering the shockresistance. As an amount of addition, it is made as being in the rangeof 0-5% (calculated as solid content), if it exceeds over 5%, a probleminvolving with the surface precision occurs and the water resistance ofthe primer film is lowered.

The thermosetting resin such as melamine resin and the like can be usedfor adjusting the coating film hardness. As an amount of addition, it isin the range of 0-20% (calculated as solid content), and if it exceedsover 20%, it results in a malfunction involving with the shockresistance.

B. (a) It is presumed as prerequisite requirement that for a hard coatcomposition of the present invention, the hydrolysate of thealkoxysilane mainly consisted of alkoxysilane containing monoepoxyorganic group is made as a matrix formation ingredient and titania basedmetal oxide complex particle is made as an optical interference controlagent.

(b) The most significant characteristic of the present invention is inthat the titania based metal oxide complex particle is consisted of TiO₂as the main body, SiO₂ as the major sub-ingredient and further, ZrO₂ andK₂O as trace sub-ingredient.

Concretely, the specification of the titania based complex particle isnot particularly limited if a high refractive index correspondingcharacteristics (refractive index enhancement action) is obtained and itis in the range of exerting the action of the above-described opticalinterference suppression agent.

(1) The average particle diameter of the complex particle is made asbeing in the range of 1-100 nm, and desirably 2-50 nm, and furtherdesirably, in the range of 4-25 nm. If the particle diameter of thecomplex particle is small, the abrasive resistance is not only capableof being expected to be enhanced, but also the aggregation is easilyoccurred, and the uniformity of the coating film is likely to beinhibited. Conversely, if the particle diameter of the complex particleis large, the coating film is easily to be milkiness, and the appearanceis likely to be damaged.

(2) The composition of the respective metal oxides are defined tosatisfy the respective weight ratios as follows:

SiO₂/TiO₂=0.1900-0.2100, desirably, 0.1950-0.2050.

ZrO₂/TiO₂ =0.0015-0.023, desirably, 0.002-0.020.

K₂O/TiO₂=0.0012-0.012, desirably. 0.002-0.010.

SiO₂/ZrO₂/K₂O=100/0.789/0.632-100/10.953/5.714, desirably,100/1.026/1.026-100/9.756/4.878.

The metal oxide complex particle is constituted by integrally couplingSiO₂, ZrO₂ and K₂O to TiO₂. The desirable form at this time is definedas replacement type solid solution in which the respectivesub-ingredients are uniformly melted together to TiO₂.

Now, SiO₂ which is the major sub-ingredient exerts an action not onlyfor increasing the miscibility with silane compound (alkoxysilanehydrolysate) in preparing coating but also an action for enhancing thelight resistance of the coating film. In the case where the ratio of theSiO₂ is large, the action for enhancing the refractive index that TiO₂has is inhibited, and a high refractive index correspondence becomesdifficult.

Moreover, ZrO₂and K₂O which are trace sub-ingredients do notsynergetically inhibit the refractive index enhancement action that TiO₂has, but exerts to suppress the optical activity of TiO₂. In the casewhere one of ZrO₂ and K₂O is excessive, the synergetical action ofsuppression of the above-described optical activity is not easilyobtained.

Therefore, the deterioration action against both coating film and theobject matter to be coated (organic glass) by near-ultraviolet ray canbe reduced.

(3) A method of manufacturing the above-described metal oxide complexparticle is performed similarly to, for example, the method described inJapanese Unexamined Patent Publication No. Hei 2-178219 gazette.Specifically, after TiO₂ hydration sol and ZrO₂/K₂O hydration sol areprepared and deflocculation is performed to it, resolved by addinghydrogen peroxide, and further, hydrolyzed at a high temperature byadding silicic acid dispersion liquid. The above-described silicic aciddispersion liquid is prepared, for example, by dealkalizing analkali-silicic acid aqueous solution. The above-described hydrosate is adispersion liquid of the particle. It is desirable that this particledispersion liquid is purified and processed by an ion exchange method, areverse osmosis method, an ultrafiltration method, a vacuum vapordeposition method.

It should be noted that it is desirable that the above-described complexparticle is surface-reformed with a silane coupling agent and used. Inthis way, the miscibility with the silane compound is further enhancedby surface-reforming the metal oxide complex particle, in the viewpointof the esthetic appearance after the film coating, the cloudiness can bereduced. The term “surface reforming” is referred to a processing bywhich the disperse character of the complex particle is made to bebetter by blocking hydroxyl group remained in TiO₂, ZrO₂, SiO₂ and K₂Ousing the silane coupling agent. This surface reforming can be carriedout by the method of common use. For example, it is performed by dippingin the alcohol solution into which the following organic silane compoundis resolved.

As a silane coupling agent (surface reforming agent),tetramethoxysilane, methyltrimethoxysilane, trimethylchlorosilane,vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropylmethyldiethoxysilane and the like can be preferablyused.

(4) The blending amount of this complex particle is made as 10-500portions with respect to 100 portions of the above-described totalamount of alkoxysilane, and desirably, in the range of 20-200 portions,and further, desirably, in the range of 40-100 portions.

In the case where the relevant metal oxide complex particle is slight,the high refractive index base material correspondence becomes difficultas well as the sufficient coating film hardness cannot be obtained,conversely, in the case where it is much, the coating film milkinessphenomenon and the poor appearance due to the cracks at the time whenits hard coat coating film is hardened (thermal polymerization) areeasily occurred.

(c) The matrix formation ingredient in a hard coat composition of thepresent invention is consisted of (1) hydrolysate of alkoxysilane, and(2) organic metal compound as a hardening agent as the majoringredients.

(1) The above-described alkoxysilane is consisted of trialkoxysilanemonoepoxy group as the main body, and usually used withtetraalkoxysilane in combination.

Then, the above-described trialkoxysilane is expressed by the followinggeneral formula (1):

General Formula (1)

(where R¹ represents H or CH₃, R² represents alkylene group having thenumber of carbon atoms of 1-4, and R³ represents alkyl group having thenumber of carbon atoms of 1-4), or, it is desirable that it is consistedof one or more than one species selected from the group expressed by thefollowing general formula (2):

General Formula (2)

(where R¹ represents alkylene group having the number of carbon atoms of1-4, and R² represents alkyl group having the number of carbon atoms of1-4)

As a concrete example of the above-described general formula (1), thefollowings can be listed. Among these compounds, particularly, R² havingthe number of carbon atoms of 3-4 is desirable.

glycidoxymethyltrimethoxysilane,

glycidoxymethyltriethoxysilane,

glycidoxymethyltripropoxysilane,

glycidoxymethyltributoxysilane,

α-glycidoxyethyltrimethoxysilane,

α-glycidoxyethyltriethoxysilane,

α-glycidoxyethyltripropoxysilane,

α-glycidoxyethyltributoxysilane,

β-glycidoxyethyltrimethoxysilane,

β-glycidoxyethyltriethoxysilane,

β-glycidoxyethyltripropoxysilane,

β-glycidoxyethyltributoxysilane,

α-glycidoxypropyltrimethoxysilane,

α-glycldoxypropyltriethoxysilane,

α-glycidoxypropyltrlpropoxysilane,

α-glycldoxypropyltrlbutoxysilane,

β-glycidoxypropyltrimethoxysilane,

β-glycidoxypropyltriethoxysilane,

β-glycidoxypropyltripropoxysilane,

β-glycidoxypropyltributoxysilane,

γ-glycidoxypropyltrimethoxysilane,

γ-glycidoxypropyltriethoxysilane,

γ-glycidoxypropyltripropoxysilane,

γ-glycidoxypropyltributoxysilane,

α-glycidoxybutyltrimethoxysilane,

α-glycidoxybutyltriethoxysilane,

α-glycidoxybutyltripropoxysilane,

α-glycidoxybutyltributoxysilane,

β-glycidoxybutyltrimethoxysilane,

β-glycidoxybutyltriethoxysilane,

β-glycidoxybutyltripropoxysilane,

β-glycidoxybutyltributoxysilane,

γ-glycidoxybutyltrimethoxysilane,

γ-glycldoxybutyltriethoxysilane,

γ-glycidoxybutyltripropoxysilane,

γ-glycidoxybutyltributoxysilane,

δ-glycidoxybutyltrimethoxysilane,

δ-glycidoxybutyltriethoxysilane,

δ-glycidoxybutyltripropoxysilane,

δ-glycidoxybutyltributoxysilane,

β-methylglycidoxymethyltrimethoxysilane,

β-methylglycidoxymethyltriethoxysilane,

β-methylglycidoxymethyltripropoxysilane,

β-methylglycidoxymethyltributoxysilane,

β-methyl-α-glycidoxyethyltrimethoxysilane,

β-methyl-α-glycidoxyethyltriethoxysilane,

β-methyl-α-glycidoxyethyltripropoxysilane,

β-methyl-α-glycidoxyethyltributoxysilane,

β-methyl-β-glycidoxyethyltrimethoxysilane,

β-methyl-β-glycidoxyethyltriethoxysilane,

β-methyl-β-glycidoxyethyltripropoxysilane,

β-methyl-β-glycidoxyethyltributoxysilane,

β-methyl-α-glycidoxypropyltrimethoxysilane,

β-methyl-α-glycidoxypropyltriethoxysilane,

β-methyl-α-glycidoxypropyltripropoxysilane,

β-methyl-α-glycidoxypropyltributoxysilane,

β-methyl-β-glycidoxypropyltrimethoxysilane,

β-methyl-β-glycidoxypropyltriethoxysilane,

β-methyl-β-glycidoxypropyltripropoxysilane,

β-methyl-β-glycidoxypropyltributoxysilane,

β-methyl-γ-glycidoxypropyltrirethoxysilane,

β-methyl-γ-glycidoxypropyltriethoxysilane,

β-methyl-γ-glycidoxypropyltripropoxysilane,

β-methyl-γ-glycidoxypropyltributoxysilane,

β-methyl-α-glycidoxybutyltrimethoxysilane,

β-methyl-α-glycidoxybutyltriethoxysilane,

β-methyl-α-glycidoxybutyltripropoxysilane,

β-methyl-α-glycidoxybutyltributoxysilane,

β-methyl-β-glycidoxybutyltrimethoxysilane,

β-methyl-β-glycidoxybutyltriethoxysilane,

β-methyl-β-glycidoxybutyltripropoxysilane,

β-methyl-β-glycidoxybutyltributoxysilane,

β-methyl-γ-glycidoxybutyltrimethoxysilane,

β-methyl-γ-glycidoxybutyltriethoxysilane,

β-methyl-γ-glycidoxybutyltripropoxysilane,

β-methyl-γ-glycidoxybutyltributoxysilane,

β-methyl-δ-glycidoxybutyltrimethoxysilane,

β-methyl-δ-glycidoxybutyltriethoxysilane,

β-methyl-δ-glycidoxybutyltripropoxysilane, and

β-methyl-δ-glycidoxybutyltributoxysilane.

As concrete examples of the above-described general formula (2), thefollowings can be listed. Among these compounds, particularly, R¹ havingthe number of carbon atoms of 2-4 is desirable.

(3, 4-epoxycyclohexyl) methyltrimethoxysilane,

(3, 4-epoxycyclohexyl) methyltriethoxysilane,

(3, 4-epoxycyclohexyl) methyltripropoxysilane,

(3, 4-epoxycyclohexyl) methyltributoxysilane,

(3, 4-epoxycyclohexyl) ethyltrimethoxysilane,

(3, 4-epoxycyclohexyl) ethyltriethoxysilane,

(3, 4-epoxycyclohexyl) ethyltripropoxysilane,

(3, 4-epoxycyclohexyl) ethyltributoxysilane,

(3, 4-epoxycyclohexyl) propyltrimethoxysilane,

(3, 4-epoxycyclohexyl) propyltriethoxysilane,

(3, 4-epoxycyclohexyl) propyltripropoxysilane,

(3, 4-epoxycyclohexyl) propyltributoxysilane,

(3, 4-epoxycyclohexyl) butyltrimethoxysilane,

(3, 4-epoxycyclohexyl) butyltriethoxysilane,

(3, 4-epoxycyclohexyl) butyltripropoxysilane, and

(3, 4-epoxycyclohexyl) butyltrlbutoxysilane.

As tetraalkoxysilane with which the above-described trialkoxysilane isused, it is desirable that one or more than one species selected fromthe group indicated by the following general formula (3) is used.

Si (OR¹)₄  

General Formula (3)

(where R¹ represents alkyl group having the number of carbon atoms of1-4)

More concretely, tetraethoxysilane, tetramethoxysilane,tetrapropoxysilane, tetrabutoxysilane and the like can be listed.

The hydrolysate of the above-described alkoxysilane is prepared bycarrying out the process that a drop of dilute acid of 0.01-0.1 N isadded to alkoxysilane in the presence of lower alcohol such as methanol,ethanol and the like and then hydrolysis is performed. As a dilute acid,concretely, hydrochloric acid, sulfuric acid, phosphoric acid, aceticacid, formic acid, oxalic acid, sulfonic acid and the like can be used.

Then, the blending ratio of the above-described tetraalkoxysilane to theabove-described trialkoxysilane containing epoxy is made as being 5.3-25weight portions of tetraalkoxysilane to 100 weight portions oftrialkoxysilane. If the blending ratio is out of this range, thesufficient coating hardness and the excellent appearance are not easilyobtained. Specifically, in the case where tetraalkoxysilane isexcessive, the poor appearance due to the cracks occurs at the time whenthe thermal polymerization is performed following coating film onorganic lens, and in the case where it is too little, sufficient coatingfilm hardness is not easily obtained.

(2) As the above-described organic metal compound (metal chelate), oneor more than one species selected from any of Cr (III), Co (III), Fe(III), Zn (II), In (III), Zr (IV), Y (III), Al (III), Sn. V, and Ti (II)with which a chelating agent selected from ethylenediamine-tetraaceticacid, hexafluoroacetylacetone, trifluoroacetylacetone, acetylacetone andmethyl acetoacetate coordinates, can be used.

Among these, iron (III) acetylacetone, iron (III)hexafluoroacetylacetone, tin acetylacetone, vanadyl acetyl acetone,indium (III) acetylacetone, zirconium (IV) acetylacetone, second cobalt(III) acetylacetone, titanium (II) acetylacetone and aluminium (III)acetylacetone are desirable.

The amount of addition of this organic metal compound is made as being0.1-10 portions (desirably, 0.3-5 portions) with respect to 100 portionsof the total alkoxysilane hydrolisate (solid content).

It should be noted that alkoxysilane compound, if it is hydrolyzed,usually is reduced by 25-35% as weight.

Furthermore, trace of ultraviolet ray absorbent, antioxidant agent,disperse dye, antistatic agent, surfactant is capable of being added toa hard coat composition of the present invention for the purpose ofimproving the coating film character and appearance performanceaccording to the necessary.

Concretely, as an ultraviolet absorbent, benzotriazol based absorbent,benzophenon based absorbent and the like is capable of being used,hindered amine based absorbent is useful when it is used in combinationwith an antioxidant agent. As a disperse dye, aqueous disperse dye isused.

As a surfactant, it is desirable that nonionic surfactant in which thehydrophobic group is consisted of dimethylsilicone oil and thehydrophilic group is consisted of polyether is used for the purpose ofenhancing the smoothness and antistatic characteristics. Thesecharacteristics are obtained by fluorine based surfactant and the like,however, among fluorine based surfactants, particularly as tomacromolecules, in the case where these are used in combination withTiO₂/SiO₂/ZrO₂/K₂O of metal oxide complex particles which are (C)ingredients, since these have also a characteristic easily aggregatingthe relevant metal oxide complex particles, it requires care when theseare used. Moreover, as an amount of usage of surfactant, 0.01-0.5portions (desirably, 0.03-0.3 portions) of a surfactant is used withrespect to 100 portions of the hard coat composition (the total weightof matrix formation ingredients and metal oxide complex particles). Inthe case where it is less than 0.01 portions, the sufficient smoothnessand antistatic characteristics are not easily obtained, and in the casewhere it exceeds over 0.5 portions, the cloudiness is easily occurred atthe time of forming film even if a silicone based surfactant is used.

C. An optical element of the present invention is characterized in thatthe above-described primer layer is intervened between the foregoingorganic glass and the silicone based hardening coating film in theoptical element which is constructed by forming a silicone basedhardening coating film on the organic glass.

Moreover, an optical element of the present invention has a hard coatlayer which is formed by the hard coat composition constituted asabove-described on an organic glass base material indicating more than1.66 of the refractive index.

Now, as an organic glass, for example, an organic glass obtained bypolymerizing and reacting (i) an active hydrogen compound consisted ofhydroxy compound having polyol, polythiol and mercapto group, and (ii)one or more species selected from the group of polyisothiocyanatecompounds and isothiocyanate compounds having an isocyanate group can bepreferably used (see for example, Japanese Unexamined Patent PublicationNo. Hei 2-167330, gazette). For this isothiocyanate compound, a compoundhaving more than one piece of sulfur atoms in addition to anisothiocyanate group are also used.

The above-described polyisothiocyanate is referred to a compound havingmore than one of —NCS groups in one molecule, and it may be availableeven if it has one or more piece of sulfur atoms in addition to anisothiocyanate group.

For example, fatty isothiocyanate such as 1, 2-diisothiocyanate ethane,1, 3-diisothiocyanate propane, 1, 4-diisothiocyanate butane, 1,6-diisothiocyanate hexane, p-phenylenediisopropylidinediisothiocyanateand the like, alicyclic isothiocyanate such ascyclohexanediisothiocyanate and the like, isothiocyanate containing aheterocycle such as 1, 2-diisothiocyanate benzene, 1, 4-diisothiocyanatebenzene, 2, 4-diisothiocyanate toluene, 2, 5-diisothiocyanate-m -xylene,4, 4-diisothiocyanate-1, 1-biphenyl, 1, 1-methylene bis(4-isothiocyanate benzene), 1, 1-methylene bis(4-isothiocyanate-2-methylbenzene), 1, 1-methylene bis(4-isothiocyanate-3-methylbenzene) and the like, and further,carbonylisothiocyanate such as hexanedioel isothiocyanate,nonanedioeldiisothiocyanate, and carbonic diisothiocyanate and the likecan be preferably used.

As a polyisothiocyanate containing one or more pieces of sulfur atoms inaddition to an isothiocyanate group, fatty isothiocyanate containingsulfur such as thio bis (3-isothiocyanate propane), thio bis(2-isothiocyanate ethane), dithio bis (2-isothiocyanate ethane) and thelike;

aromatic isothiocyanates containing sulfur such as1-isothiocyanate-4-((2-isothiocyanate ethyl) sulfonyl) benzene, thio bis(4-isothiocyanate benzene) and the like; and

Heterocyclic compound containing sulfur such as thiophene-2,5-diisothiocyanate, 1, 4-dithiane-2, 5-diisothiocyanate and the like canbe preferably used.

As an isothiocyanate compound having the foregoing isocyanate group, forexample, fatty or alicyclic compound such as1-isocyanate-3-isothiocyanate propane, 1-isocyanate-5-isothiocyanatepentane, 1-isocyanate-6-isothiocyanate hexane,1-isocyanate-4-isothiocyanate cyclohexane and the like; and aromaticcompound such as 1-isocyanate-4-isothiocyanate benzene and the like canbe preferably used.

For the above-described active hydrogen compound, one or more speciescan be selected from hydroxy compounds having polyol, polythiol, andmercapto groups.

As a polyol, for example, fatty polyol such as ethylene glycol,diethylene glycol, propylene glycol, dipropylene glycol, butyleneglycol, neopentyl glycol, glycerin, trimethylol ethane,trimethylolpropane, butane triol, 1, 2-methylglucoside, pentaerythritol,dipentaerythritol, tripentaerythritol, sorbitol, erytritol, slatol,ribitol, arabinitol, xylitol, allitol, mannitol, dorsitol, iditol,glycol, inositol, hexanetriol, triglycellose, diglyperole, triethyleneglycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate,cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol,cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol,bicyclo (4, 3, 0)-nonanediol, dicyclohexanediol, tricyclo (5, 3, 1. 1)dodecanediol, bicyclo (4, 3, 0)nonanedimethanol, tricyclo(5, 3, 1, 1)dodecanediethanol, hydroxypropyltricyclo (5, 3, 1, 1) dodecanol, spiro(3, 4) octanediol, butylcyclohexanediol, 1, 1-bicyclohexyledendiol,cyclohexanetriol, maltitol, lactitol and the like;

aromatic polyol such as dihydroxynaphthalene,trihydroxynaphthalene,tetrahydroxynaphthalene, dihydorxybenzene,benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol,trihydroxyphenanthrene, bisphenol A, bisphenol F, xylileneglycol, di(2-hydroxyethoxy) benzene, bisphenol A-bis-(2-hydroxyethylether),tetrabrominebisphenol A-bis-(2-hydroxyethylether) and the like;

polyol halide such as dibromoneopentyl glycol;

macromolecule polyol such as epoxy resin and the like; and further,

addition reaction products of organic acids such as oxalic acid,glutamic acid, adipic acid, acetic acid, propionic acid,cyclohexanecarboxylic acid, β-oxocyclohexanepropionic acid, dimericacid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionicacid, 2-bromo glycol, dicarboxycyclohexane, pyromellitic acid,butanetetracarboxylic acid, bromophthalic acid and the like, theforegoing polyol, and alkyleneoxide such as ethyleneoxide,propyleneoxide and the like;

addition reaction products of alkylenepolyamine and alkyleneoxide suchas ethyleneoxide, propyleneoxide and the like;

polyols containing a sulfur atom such as bis-(4-(2-hydroxyethoxy)phenyl) sulfide, bis-(4-(2-hydroxypropoxy) phenyl) sulfide and compoundsto which propyleneoxide is added, di-(2-hydroxyethyl) sulfide), 1, 2-bis(2-hydroxyethylmercapto) ethane, 1, 5-dihydroxy-1, 4-dithiane and thelike can be preferably used.

Moreover, as a polythiol, fatty polythiol such as methanedithiol,1,2-ethanedithiol, 1,1-propanethiol, 1, 1-cyclohexanedithiol, 2,2-cyclohexanedithiol, diethylene glycolbis (2-mercaptacetate), ethyleneglycol bis (2-mercaptoacetate) and the like;

aromatic polythiols such as 1, 2-dimercaptobenzene, 1. 2,3-trimercaptobenzene, 1, 2, 3-tris (mercaptoethyleneoxy) benzene, 1, 2,3, 5-tetramercaptobenzene, 1, 4-naphthalenedithiol, 2,4-dimethylbenzene-1, 3-dithiol and the like;

halogen substitution aromatic polythiol such as chlorine substitutionproducts such as 2, 5-dichlorobenzene-1, 3-dithiol, 3, 4.5-tribromine-1. 2-dimercaptobenzene and bromine substitution productsand the like;

polythiols containing a heterocycle such as 2-methylamino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4, 6-dithiol-sym-triazine andthe like;

aromatic polythiols containing a sulfur atom in addition to mercaptogroup such as nuclear alkylate such as 1, 2-bis (mercaptomethylthio)benzene and the like;

fatty polythiols containing a sulfur atom in addition to a mercaptogroup such as bis (mercaptomethyl) sulfide, bis (mercaptomethylthio)methane, tetrakis (mercaptomethylthiomethyl)methane and the like, oresters of thioglucolic acid and mercaptopropionic acid of these,hydroxymethylsulfide bis (2-mercaptoacetate), 2-mercaptoethylether bis(2-mercaptoacetate), 1, 4-dithiane-2, 5-diol bis (2-mercaptoacetate),thioglycolicacidbis (2-mercaptoethyl ester) and the like; and

heterocyclic compounds containing a sulfur atom in addition to mercaptogroup such as 3, 4-thiophenedithiol and the like can be preferably used.

Moreover, as a hydroxy compound having a mercapto group (thiol group),

2-mercaptoethanol, 3-mercapto-1, 2-propanediol, glycerin di(mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroxynon, 4-mercaptophenol, 3,4-dimercapto-2-propanol, 1, 3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1, 3-butanediol, pentaerythritoltris (3-mercaptopropionate), pentaerythritol mono(3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate),pentaerythritol tris (thioglycol), pentaerythritol pentakis(3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl)methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene,4-hydroxy-4-mercaptodiphenylsulfone, 2-(2-mercaptoethylthio) ethanol,dihydroxyethylsufide mono (3-mercaptopropionate), dimercaptoethane mono(salicylate), hydroxyethylthiomethyl tris (mercaptoethylthio) methaneand the like are listed.

Furthermore, halogen substitution product of these active hydrogencompounds (ex; chlorine substitution products and bromine substitutionproducts) can be also used. These are capable of being used singly andone or more species of these can be also mixed and used in combination.

Then, an organic glass used for an optical element of the presentinvention is obtained by polymerizing and reacting the above-describedisothiocyanate compound and active hydrogen compound so that thefunctional group molar ratio of (NCO+NCS)/(OH+SH) is usually in therange of 0.5-3.0, desirably in the range of 0.5-1.5, more desirably inthe range of 0.8-1.2.

As the other organic glass indicating a high refractive index, anorganic glass having two or more of the structure indicated by thefollowing general formulation (4), which is obtained by polymerizing andhardening episulfide compound having a cyclic skeleton can be preferablyused (for example, see Japanese Unexamined Patent Publication No. Hei9-71580, gazette).

General Formula (4)

(where X represents S or O, the number of pieces of S is on average morethan 50% with respect to the total of S and O which constitute threemembered ring).

Concretely, an organic glass which is represented by the followinggeneral formula (5) can be preferably used.

General Formula (5)

(where X represents

(Y represents S r O), a, b, c, d and e are integer satisfying thefollowing equations: a+b+c+d=4; a, b=0 or 1; c, d=0, 1, 2, 3 or 4; e=0,1, 2 or 3)

As a method of coating the above-described object matter to be coated(organic glass), brushing coating method, dipping coating method, rollercoating method, spray coating method, spin coating method and the likecan be listed. Moreover, as an example of drying-hardening conditions,the conditions under which the coating is performed at 60° C.-150° C. ispreferable, and particularly preferably at 80° C.-120° C. for 1-5 hours,and the thickness of the coated film obtained after hardening is in therange of 0.5 μm-20 μm.

It is desirable that before the coating of a composition of the objectmatter to be coated of the present invention is performed, a degreasewashing by an acid-alkali washing solvent, plasma processing, ultrasoniccleaning and the like are performed.

D. It is desirable that a reflection prevention film of an inorganicsubstance based one is further laminated on the foregoing hard coatlayer.

As a reflection prevention film capable of forming on the hardeningcoating film, inorganic matters such as a metal simple body, a metaloxide, metal fluoride and the like are listed. As a metal oxide, SiO₂,SiO, TiO₂, Ta₂O₅, CeO₂, Nb₂O₅, Sb₂O₃, ZrO₂, Al₂O₃ and Y₂O₃ can belisted, and a single or more species of them can be appropriatelyselected and used. As a metal fluoride, MgF₂ and the like can be listedfrom them and a single and/or more species of them can be appropriatelyselected and used. Moreover, by utilizing non-transparent metalzirconium and TiO, Ti₂O₃, Ti₃O₅ and the like as a starting raw material,the film is capable of being formed by the method described later.

For a reflection prevention film provided on the hard coat film, as afundamental film configuration, there are a two-layers type in which λ/2and λ/4 of the thickness of the optical films are in turn laminated fromthe side of the substrate (hard coat), and a three-layers type in whichλ/4, λ/2 and λ/4 of the thickness of the optical films are in turnlaminated from the side of the substrate and so forth, however, sincethe wavelength area of the reflection prevention can be widened, thethree-layers type is preferable.

In the present invention, as a reflection prevention film, a film inwhich the design center wavelength λ is made as being targeted in therange of 450-550 nm, a medium refractive index layer having an opticalfilm thickness of 0.19-0.29 λ, a high refractive index layer having anoptical film thickness of 0.42-0.58 λ, and a low refractive index layerhaving an optical film thickness of 0.19-0.29 λ are in turn formed fromthe side of the foregoing hard coat layer is desirable. This is becausea wavelength area with which the reflection prevention film is capableof corresponding can be widened.

The film thickness and refractive index of the respective layers aredifferent depending on the refractive index of the hard coat film layingbeneath or below. As a concrete example, each of optical film thicknessis made as being in the range of 100-140 nm for the medium refractiveindex layer, in the range of 220-260 nm for the high refractive indexlayer, and in the range of 100-140 nm of the low refractive index layer,and the constitutions in which inorganic materials indicated below areemployed can be used.

(α) SiO₂/ZrO₂: 1/4 λ (medium refractive index layer)

ZrO₂: 1/2 λ (high refractive index layer)

SiO₂: 1/4 λ (low refractive index layer)

(β) SiO₂/TiO₂: 1/4 λ (medium refractive index layer)

TiO₂: 1/2 λ (high refractive index layer)

SiO₂: 1/4 λ (low refractive index layer)

In the case where there is no substance having a suitable refractiveindex, an equivalent film in which one or more layers having differentrefractive indexes are used can be used. It is desirable that the mediumrefractive index layer in the above-described concrete example is formedby the equivalent film method in which the substances used for the highrefractive index layer and the low refractive index layer are used andthe film is formed.

Now, the term equivalent film methods is referred to a method in whichif a substance having the desired refractive index from the requirementon the design of a reflection prevention film is absent, a substancehaving a higher refractive index than that substance and a substancehaving a lower refractive index than that substance are alternatelyformed into films making an optically equivalent multiplayer film tosubstitute the substance.

E. When a reflection prevention film of the present invention is formedinto a film, in order to enhance the adhesive force of the reflectionprevention film to the hard coat film, it is desirable that the surfaceprocessing of the hard coat film is performed as a prior processing. Asa concrete example, a drug processing using acid, alkali, argon oroxygen plasma processing by a high frequency, and oxygen ion or argonion irradiation processing by an ion gun are listed.

Among the above-described ones, it is preferable that particularly, anion cleaning processing is performed since excellent surface can beobtained.

Moreover, as a method of forming a reflection prevention film, a methodin which the above-described inorganic powder particle is vapordeposited by utilizing dry-plating method such as vacuum vapordeposition, spattering, ion plating and the like is capable of beingused.

At least the formation of a high refractive index layer is performed byvapor depositing by utilizing an ion beam assist method. For the otherfilms, needless to say, the ion beam assist method may be used, or theother physical vapor deposition method may be used.

It should be noted that for “ion cleaning” and “ion beam assist”, thesehave been described in detail in Japanese Unexamined Patent PublicationNos. Hei 10-123301 and Hei 11-174205 gazettes and the like.

F. The fundamental constitution of a composition for an organic glassdyeing includes a non-aqueous dye, a size agent (dye supporting resin)and dye resolving agent.

It should be noted that in the following description, an organic glassbase material which is to be an object to be dyed or an organic glassbase material having a hard coat layer is referred to as “the objectbase material to be dyed”.

The reason why a non-aqueous dye is used is that a material whosesublimation tendency is high is easily obtained as well as its dyeingproperty (migration to organic glass) to an organic glass having a highrefractive index is excellent.

Where the level of sublimation tendency is not necessarily a levelindicating a sublimation tendency at the ordinary temperature/under theatmospheric pressure, but may be a level indicating a sublimationtendency in the presence of heating atmosphere and/or in vacuo.

As a non-aqueous dye, a disperse dye for universal use or a solvent dyecan be preferably used.

As a disperse dye, “Sumikaron” (made by Sumitomo, Chemical, Co., Ltd.);“Diacelliton”, “Dianix”, “Samaron” (made by Mitubishi ChemicalInd.-Heochest, Co., Ltd.); “Kayalon Polyester” (mad by Nippon Kayaku,Co., Ltd.); “Miketon Polyester” (made by Mitsui Chemical, Co., Ltd.) andthe like, which are commercially available in these trade names,respectively, can be listed.

As a solvent dye, “Spilit” (made by Sumitomo Chemical, Co., Ltd.);“Orient Oil” (made by Orient Chemical, Co., Ltd.), “Mitsui PS” (made byMitsui Chemical, Co., Ltd.) and the like, which are commerciallyavailable in these trade names, respectively, can be listed.

An ultraviolet ray absorbent and a fluorescent whitening agent (which isa kind of water insoluble dyes, respectively) exhibiting the sublimationtendency comparable to these dyes can be added to the disperse dyes andthe solvent dyes which are the water insoluble dyes described above.

The content of the above-described ultraviolet ray absorbent andfluorescent whitening agent is made as being in the range of 0.1-50 wt%, and desirably 1-20 wt % of the total amount of weight of the waterinsoluble dyes to which these absorbent and agent have been added.

In the case where a composition for dyeing containing these ultravioletray absorbent and fluorescent whitening agent is applied to a lens ofthe glasses which is to be formed by an organic glass, these functionscan be conferred at the same time that it is dyed. Specifically, whenthe glasses are used, the fashionability of the glasses can be enhancedas well as the eyes can be protected from ultraviolet rays.

As to an ultraviolet ray absorbent, there are no particular limitationsif it has the sublimation tendency, therefore, benzophenone based,benzotriazole based, cyanoacrylate based, salicylate based ultravioletray absorbents and the like are capable of being used.

As a fluorescent whitening agent, diaminostilbenedisulfonic acid based,imidazole based, coumalin based, triazole based fluorescent whiteningagents and the like are capable of being used.

As a sizing agent (pasting agent: dye carrying and supporting agent),from the viewpoints of the dye carrying and supporting property to a dyeand the adhesiveness to a base material having a high refractive index,acrylic resins are used.

The blending ratio of the relevant sizing agent (acrylic resin) to theabove-described dye (containing ultraviolet absorbent, fluorescentwhitening agent) is made in the range of the sizingagent/dye=60/40-5/95, desirably 40/60-10/90. If the sizing agent is toolittle, the dye does not easily adhere to the base material, conversely,if it is too much, the dyeing property is lowered and it takes a time todye (migration).

Concretely, a single or more than two species appropriately selectedfrom the resin ingredients exemplified below can be used.

Now, as an acrylic resin, it is desirable to use a resin whose glasstransition temperature (Tg) is in the range of 80-120° C., desirably100-110° C. average molecular weight (Mn) is in the range of100,000-200,000, desirably 50,000-150,000. The acrylic resin in theseranges are desirable since it is excellent for solubility and dyesupporting property to the dye resolving agent to be described later,and the adhesion property and clearance ratio to the base material.

As a resin ingredient, acrylic resins such as methylpolyacrylic acid,ethylpolyacrylic acid, propylpolyacrylic acid, n-butylpolyacrylic acid,poly (methyl-α-cyanoacrylate), poly (methyl-α-chloroacrylate) and thelike; and,

methacrylic resins such as methylpolymethacrylic acid,ethylpolymethacrylic acid, n-propylpolymethacrylic acid, n-butylpolymethacrylic acid, t-butylpolymethacrylic acid,n-hexylpolymethacrylic acid, 2-ethylhexylpolymethacrylic acid,laurylpolymethacrylic acid, i-bornyl polymethacrylic acid, stearylpolymethacrylic acid, ethoxyethyl polymethacrylic acid and like can belisted.

As the above-described resolving agent, an organic solvent whosesolubility parameter (SP) value is in the range of 8-11, desirably 9-10is used. In the case where the SP value is out of the range describedabove, since the mutual solubility of the resin, the dye and the solventis lowered, the dyeing to the concentration to be aimed at cannot beachieved and it leads to the poor appearances such as non-uniformity orthe like.

The dye resolving agent described above is selected considering the factthat the resolving agent does not influence on the surface of theorganic glass base material and/or hard coat layer (no dry spot on thesurface).

Concretely, a single or more than two species appropriately selectedfrom the organic solvents listed below can be used (SP value isindicated in parenthesis).

Aromatic hydrocarbons such as benzene (9.15), toluene (8.90), o-xylene(9.00), m-xylene (8.80), p-xylene (8.75), ethylbenzene (8.80),naphthalene (9.90), tetralin (9.50), n-propylbenzene (8.65),i-propylbenzene (8.86), mesitylene (8.80), p-cemene (8.85) and the like;and,

Ketones such as acetone (10.00), methylethylketone (9.30), diethylketone(8.8), dibutylketone (8.1), methyl-n-propylketone (8.7),methyl-n-butylketone(8.6), methyl-i-amylketone (8.50),methylhexylkentone (8.45), cyclohexanone (9.90), acetophenone (9.68) andthe like; and,

ethers such as methylal (8.52), furan (9.09), β-β-dichloroethylether(9.80), dioxane (10.00), tetrahydrofuran (9.90), ethylcellosolve (9.90)and the like are listed.

Since the organic solvent containing at least ethers and/or ketones,these are excellent in resolving property of water insoluble dye, anddoes not easily cause the surface of the object base material to be dyed(organic glass or hard coat layer) to be dry spot, these are desirable.

Furthermore, since these solvents make the dye having the sublimationtendency dispersed or resolved stabilize it in the paint and enhance thesmoothness as a paint, a silicone based surfactant or fluorine basedsurfactant can be also blended.

Upon manufacturing a composition for dyeing by blending theabove-described raw materials, the concentration of the dye in thecomposition of the dyeing is made as being in the range of 0.01-50 wt %,desirably 0.1-40 wt %. If the concentration of the dye is too high, thesolubility, disperse property is lowered, the dye not capable of beingresolved and dispersed is transcribed to the lens as it is, and it leadsto the poor appearance. Moreover, conversely, if the concentration istoo low, the dyeing can be scarcely carried out.

The concentration of the sizing agent in the composition for dyeing ismade as being in the range of 0.01-40 wt %, desirably 0.1-20 wt %. Ifthe concentration of the sizing agent is too low, a sufficient filmadhesion thickness for migrating the dye is not easily obtained, andconversely, if it is too high, the profile irregularity (levelingproperty) is lowered, and it causes the occurrence of the non-uniformityof dyeing.

Then, the dyeing of the object base material to be dyed of the presentinvention is carried out by forming an adhesive film by coating theabove-described paint for dyeing on the object base material to be dyed(pasting is performed), by sublimating the dye and by transferring(migrating) the dye to the object base material to be dyed.

As a method of adhering (coating) the paint for dyeing on the objectbase material, there are no limitations if it can be uniformly adhered.Concretely, the known technologies, such as a spin coat method, adipping method, a brushing method, a spraying method, an inkjetrecording method and the like can be utilized. At this time, the filmthickness of adhesion is, in the case of dry film thickness, usuallymade as being in the range of 0.3-2 μm, desirably in the range of 0.5-1μm.

The sublimation of the above-described dyes usually is performed byheating processing, since the heating processing is higher thanprocessing in vacuum.

Moreover, the temperature of the heating processing is usually made asbeing in the range of about 60-200° C., desirably about 90-170° C., andfurther desirably about 100-150° C., depending on the glass transitiontemperature of the organic glass which is to be the object base materialto be dyed, the heat resistance temperature of the silicone basedhardening coating film or the sublimation pressure (sublimationtemperature) of the dye having the sublimation property in the paint fordye sublimation pressure (sublimation temperature).

If the heating processing temperature is too low, the sufficient dyeingproperty is not easily obtained, and conversely, the thermal deformationof the organic glass is likely to be occurred. It should be noted thatin this case, if the atmosphere of the pressure is reduced (usually,10-800 hPa), the heating processing temperature can be lowered, and thetime taken for the processing can be expected to be shortened.

Although the heating processing time is different depending on thedifference of the objective coloring concentration and the dyeingproperty of the object base material, it is usually made as being in therange of 10 minutes to 24 hours, preferably 30 minutes to 6 hours. It isnecessary to select both heating processing temperature and timeconsidering the fact that these factors do not have a bad influence onthe organic glass base material to be the object to be dyed or the hardcoat film (silicone based hardening coating film).

As to this heating processing means, there are no limitations, acirculatory hot stove, a far infrared radiation furnace, an electricfurnace, a dry processing using dryer and the like, a wet processing byimmersing in hot water or heated oil bath and the like are listed,however, the use of the circulatory hot stove in which there is nounevenness of the temperature within the apparatus and an organic glasscan be uniformly heated is desirable.

It should be noted that on this heating processing, if the operationdescribed below is added, a dyed organic glass having the coloringconcentration gradation could be easily obtained.

In order to obtain dyed organic glass having the coloring concentrationgradation, after the composition for dyeing is coated on the organicglass, non-uniform heating is performed to at least the coating surface.

As a method of performing the non-uniform heating, a far infraredradiation furnace, an electric furnace, a dryer, a hot water bath orheated oil bath in which the local heating is easily performed is used,the heating processing is performed so that the temperature gradation isformed with respect to at least the coated surface, or the heating timeis differentiated. By performing such a non-uniform heating, thecoloring concentration gradations can be held according to the totalheating amount.

Therefore, a far infrared radiation furnace, an electric furnace, adryer or a wet processing in which the local heating is easily performedis desirable.

As a cooling method when obtaining a dyed glass having the coloringconcentration gradation, there are no particular limitations, however,to use the air at less than 40° C. is practically preferable. Thecooling by air is capable of suppressing the migration (coloring) due tothe thermal conduction.

Since it performs the heating processing at the higher temperaturecomparing with the conventional immersion dyeing method, it enables tomake the dye permeable into the depth of the base material. Moreover, anexcellent dyeing effect can be exerted to a base material having anultra high refractive index that the dyeing is difficult by theconventional immersing dyeing method.

Moreover, when the above-described thermal processing is performed, theprevention for the blowing off the debris to the external and theprevention of scar occurring on the coating formation surface is made asan object, the thermoplastic resin may further be coated on the coatingformation surface as a protective film.

As to the above-described thermoplastic resin for protective film, thereare no particular limitations if the resin is excellent at heatresistance and the solvent resistance, and after it being a protectivefilm, the resolving and peeling off can be performed. Concretely,polyvinylbutyral, polyvinylalcohol and the like can be preferably used.

The sizing agent and the above-described protective film which isadhered on the base material after the heating processing for theabove-described migration (sublimation) are removed by immersing it intoan organic solvent, water or the like. As an organic solvent capable ofutilizing, an organic solvent having a SP value of 8-11 similarly to thesolvent used as the foregoing dye resolving agent is used.

Then, in the case where the above-described method of dyeing is used,each optical element of the present invention is capable of being dyed.

Hereinafter, the respective effects of the present invention will besummed up.

(1) The TPEE based primer composition of the present invention does notlower the heat resistance of the base material as well as the variousproperties (appearance, scraping and damaging resistance, adhesivenessand shock resistance and the like) comparable to the conventional TPUbased primer.

Furthermore, if a metal oxide particle is used in combination, thecorrespondence to the base material having a higher refractive index canbe realized.

(2) A hard coat composition of the present invention is capable ofsuppressing the optical interference in the case of a lens having anultra high refractive index by making it the constitution describedabove. In addition, the hard coat composition of the present inventiondoes neither generate the blackening phenomenon due to the ultravioletray, nor, in the case where the optical part is used for a long period,does it damage the esthetic appearance.

(3) A composition for dyeing of the present invention enables to performthe coloring at a given concentration widely ranging from lowconcentration to high concentration by combining the non-aqueous dye,the sizing agent and dye resolving agent in a specific manner, andfurther a uniform coloring organic glass without unevenness is capableof being provided.

Then, if a method of dyeing of the present invention is used, since thedye is made to be permeable to the base material at the hightemperature, color fade-out is slight comparing with the conventionalmethod. Therefore, the present invention can be applied to a basematerial having an ultra high refractive index, which has been difficultto dye.

EXPERIMENTAL EXAMPLES

Hereinafter, Examples and Comparative Examples for confirming theeffects of the present invention will be described. In the followingdescription, “portion(s)” and “%” indicating a blending unit are “weightportion(s)” and “wt %”, respectively, if there is no particular noticethereof.

The respective agents and its representative physical properties aredescribed as follows:

Colloidal silica: “methanol silica sol”, made by Nissan Chemical, Co.,Ltd., solid content concentration 30%, particle diameter 30 nm, methylalcohol solvent.

Leveling agent: “SILWET L-77”, made by Nippon Unica, Co., Ltd., siliconesurfactant.

Titanium oxide based complex particle: “Optolake 1130Z (1)”, made byCatalysts & Chemicals Ind., Co., Ltd., ZrO₂/TiO₂=0.02, SiO₂/TiO₂=0.22,particle diameter 10 nm, solid content concentration 20%, methyl alcoholsolvent, surface refining agent γ-glycidoxypropyltrimethoxysilane.

Titanium oxide based complex particle: “Optolake 1130Z (1)”, made byCatalysts & Chemicals Ind., Co., Ltd., SiO₂/TiO₂=0.2049,ZrO₂/TiO₂=0.0198, K₂O/TiO₂=0.0099, particle diameter 8 nm, solid contentconcentration 30%, methyl alcohol solvent, surface refining agenttetraethoxysilane.

Titanium oxide based complex particle: “Optolake 1130Z (2)”, made byCatalysts & Chemicals Ind., Co., Ltd., SiO₂/TiO₂=0.1986,ZrO₂/TiO₂=0.0024, K₂O/TiO₂=0.0024, particle diameter 8 nm, solid contentconcentration 25%, methyl alcohol solvent, surface refining agenttetraethoxysilane.

Leveling agent: “SILWET L-7001”, made by Nippon Unica, Co., Ltd.,silicone surfactant.

Titanium oxide based complex particle: “Optolake 1130FII”, made byCatalysts & Chemicals Ind., Co., Ltd., SiO₂/TiO₂=0.2351,Fe₂O₃/TiO₂=0.0075, particle diameter 11 nm, solid content concentration30%, surface refining agent tetraethoxysilane.

TPEE: “Pesresin A-160P”, made by Takamatsu Oil Fat, Co., Ltd. waterdisperse emulsion, solid content concentration 27%, viscosity 0.05 Pa·s,coating film surface hardness 40 (Shore hardness D), polyester/polyestertype.

Colloidal silica: “Oscar 1122G”, made by Catalysts & Chemicals Ind.,Co., Ltd., surface refining agent γ-glycidoxypropyltrimethoxysilane.

Polyurethane: “Superflex 150”, made by Dai-ichi-Kogyo Seiyaku, Co.,Ltd., solid content concentration 30%, inorganic modified, ester/ethertype.

Acrylic resin: “Dianar BR-80”, made by Mitsubishi Rayon, Co., Ltd.,Tg(glass transition temperature): 105° C., Mn: about 95000.

Disperse dye: “Sumikaron Blue-E-RPD”, Sumitomo Chemical, Co., Ltd.

Disperse dye: “Sumikaron Red-E-RPD”, Sumitomo Chemical, Co., Ltd.

Disperse dye: “Sumikaron Yellow-E-RPD”, Sumitomo Chemical, Co., Ltd.

Ultraviolet absorbent: “Ubinar D-50”, made by BASF Japan, Co., Ltd.,benzophenone based absorbent.

Surfactant: “Revenol V-700”, made by Kao Inc., hydrocarbon basedsurfactant.

Ion cleaning conditions:

Applied voltage: 200V

Charged current: 100 mA

Processing time: 90 seconds

Ion assist conditions:

Applied voltage: 600 V

Charged current: 200 mA

EXAMPLE 1

(1) Plastic Lens

Thiourethane based plastic lens having the refractive index of 1.67(commercially available)

(2) Hard Coat Processing

171 portions of γ-glycidoxypropyltrimethoxysilane, 28 portions oftetraethoxysilane, and 100 portions of methyl alcohol were added and 70portions of 0.01 N hydrochloric acid are dropped while agitating, andfurther, agitating for a night and a day, and the hydrolysate wasprepared.

405 portions of the afore-described titanium oxide based complexparticle “Optolake 1130Z (1)”, and 70 portions of 2-ethoxyethanol wereadded, and further, as a catalyst, 3 portions of aluminum (III)acetylacetone and 0.3 portion of the leveling agent “SILWET L-7001” wasadded to the relevant hydrolysate, agitated for a night and a day, andthe hard coating composition was prepared.

Next, the plastic lens obtained in the foregoing (1) was immersed insodium hydroxide aqueous solution (concentration 10%) at the temperatureof 40° C., was washed with pure water, after the draining was performed,was immersed in the composition of the foregoing hard coat composition.The lens was drawn up at the rate of 130 mm/min., then, afterpre-hardening at 95° C. for 20 minutes, the hardening was performed at110° C. for 4 hours, and the hard coat film was formed.

(3) Reflection prevention processing

The lens was set in the lens dome for rotating the lens to which thehard coat film is provided, while the vacuum chamber was heated at 60°C., exhausted up to the pressure 1.33×10⁻³ Pa (1×10⁻⁵ torr), and afteroxygen ion cleaning was performed, from the substrate side,

The first layer, SiO₂; refractive index, 1.46; optical film thickness,26 nm;

The second layer, TiO₂; refractive index, 2.37; optical film thickness,34 nm;

The third layer, SiO₂; refractive index, 1.46; optical film thickness,44 nm;

The fourth layer, TiO₂; refractive index, 2.37; optical film thickness,116 nm;

The fifth layer, SiO₂; refractive index, 1.46; optical film thickness,20 nm;

The sixth layer, TiO₂; refractive index, 2.37; optical film thickness,94 nm; and

The seventh layer, SiO₂; refractive index, 1.46; optical film thickness,135 nm; were vapor deposited in the above order. Moreover, the oxygenion assist vapor deposition was performed to Ti O₂ of the second layer,the fourth layer and the sixth layer.

EXAMPLE 2

The present Example was carried out similarly to Example 1 except forthat the composition of the hard coating was modified.

As to the hard coating composition, 100 portions of methyl alcohol wasadded to 205 portions of γ-glycidoxypropiltrimethoxy silane and 45portions of 0. 01N hydrochloric acid were dropped while agitating, andfurther agitating for a night and a day, and the hydrolysate wasprepared.

405 portions of the afore-described titanium oxide based complexparticle “Optolake 1130Z (1)”, 70 portions of diacetone alcohol wereadded, and further, as acatalyst, 3 portions of iron (III) acetylacetoneand 0.1 portion of the leveling agent “SILWET L-7001” was added,agitated for a night and a day, and the hard coating composition wasprepared.

EXAMPLE 3

(1) Plastic Lens

A thioepoxy based plastic lens having the refractive index of 1.74 wasobtained.

(2) Hard Coat Processing

136 portions of γ-glycidoxypropyltrimethoxysLlane, 10 portions oftetraethoxysilane, and 60 portions of methyl alcohol were added and 47portions of 0.01N hydrochloric acid were dropped while agitating, andfurther, agitating for a night and a day, and the hydrolysate wasprepared.

570 portions of the titanium oxide based complex particle “Optolake1130Z (2)”, and 69 portions of 2-ethoxyethanol were added, and as acatalyst, 2.2 portions of aluminium (III) acetylacetone and 0.3 portionof the leveling agent “SILWET L-7001” were added to the relevanthydrolysate, agitating for a night and a day, and the hard coatingcomposition was prepared.

Next, the plastic lens obtained in the foregoing (1) was immersed insodium hydroxide aqueous solution (concentration 10%) at the temperatureof 40° C., was washed with pure water, after the draining was performed,the plasma processing (oxygen gas, flow rate 40 cc/min., output 100W,processing time 40 seconds) was performed, immersed in the compositionof the foregoing hard coat composition. The lens was drawn up at therate of 130 mm/min., then, after pre-hardening at 95° C. for 20 minutes,the hardening was performed at 110° C. for 4 hours, and the hard coatfilm was formed.

(3) Reflection Prevention Processing

The lens was set in the lens dome for rotating the lens to which thehard coat film is provided, while the vacuum chamber was heated at 60°C., exhausted up to the pressure 1.33×10⁻³ Pa (1×10⁻⁵ torr), and afteroxygen ion cleaning was performed, from the substrate side,

The first layer, SiO₂; refractive index, 1.46: optical film thickness,26 nm;

The second layer, ZrO₂; refractive index, 2.05; optical film thickness,58 nm;

The third layer, SiO₂; refractive index, 1.46: optical film thickness,38 nm;

The fourth layer, TiO₂; refractive index, 2.37; optical film thickness,236 nm;

The fifth layer, ZrO₂; refractive index, 2.05; optical film thickness,49 nm; and

The sixth layer, SiO₂; refractive index, 1.46; optical film thickness,118 nm, were vapor deposited in the above order. Moreover, the oxygenion assist vapor deposition was performed to Ti O₂ of the fourth layer.

EXAMPLE 4

The present Example was carried out similarly to Example 3except forthat the composition of the hard coating and the configuration of thereflection prevention film were modified.

As to the hard coating composition, 60 portions of methyl alcohol wasadded to 149 portions of γ-glycidoxypropyltrimethoxysilane, 40 portionsof 0.01N hydrochloric acid were dropped while agitating, and furtheragitating for a night and a day, and the hydrolysate was prepared.

570 portions of the afore-described titanium oxide based complexparticle “Optolake 1130Z (2)”, 69 portions of diacetone alcohol wereadded, and further, as acatalyst, 3 portions of iron (III) acetylacetoneand 0.3 portion of the leveling agent “SILWET L-7001” was added to therelevant hydrolysate, agitated for a night and a day, and the hardcoating composition was prepared.

As to the reflection prevention film,

the lens was set in the lens dome for rotating the lens to which thehard coat film is provided, while the vacuum chamber was heated at 60°C., exhausted up to the pressure 1.33×10⁻³ Pa (1×10⁻⁵ torr), and afteroxygen ion cleaning was performed, from the substrate side, The firstlayer, SiO₂; refractive index, 1.46; optical film thickness, 26 nm;

The second layer, TiO₂; refractive index, 2.37; optical film thickness,40 nm;

The third layer, SiO₂; refractive index, 1.46; optical film thickness,46 nm;

The fourth layer, TiO₂; refractive index, 2.37; optical film thickness,121 nm;

The fifth layer, SiO₂; refractive index, 1.46; optical film thickness,21 nm;

The sixth layer, TiO₂; refractive index, 2.37; optical film thickness,90 nm; and

The seventh layer, SiO₂; refractive index, 1.46; optical film thickness,137 nm; were vapor deposited in the above order. Moreover, the oxygenion assist vapor deposition was performed to Ti O₂ of the second layer,the fourth layer and the sixth layer. The obtained spectral reflectionfactor property is shown in FIG. 1.

COMPARATIVE EXAMPLE 1

The present Comparative Example was carried out similarly to Example 1except for that the composition of the hard coating was modified.

As to the hard coating composition, 182 portions ofγ-glycidoxypropyltrimethoxysilane, 60 portions of tetraethoxysilane,280portions of methyl alcohol was added to the relevant hydrolysate, 47portions of 0.01N hydrochloric acid were dropped while agitating, andfurther agitating for a night and a day, and the hydrolysate wasprepared.

460 portions of the afore-described titanium oxide based complexparticle “Optolake 1130 F II”, as a catalyst, 20 portions of itaconicacid, 6 portions of dicyanamide and 0.3 portion of the leveling agent“SILWET L-7001” was added, agitated for a night and a day, and the hardcoating composition was prepared.

COMPARATIVE EXAMPLE 2

The present Comparative Example was carried out similarly to Example 2except for that the reflection prevention film was modified.

As to the reflection prevention film, the lens was set in the lens domefor rotating the lens to which the hard coat film is provided, while thevacuum chamber was heated at 60° C. exhausted up to the pressure1.33×10⁻³ Pa (1×10⁻⁵ torr), and after oxygen ion cleaning was performed,from the substrate side,

The first layer, SiO₂; refractive index, 1.46; optical film thickness,26 nm;

The second layer, TiO₂; refractive index, 2.25; optical film thickness,34 nm;

The third layer, SiO₂; refractive index, 1.46; optical film thickness,48 nm;

The fourth layer, TiO₂; refractive index, 2.25; optical film thickness,268 nm; and,

The fifth layer, SiO₂; refractive index, 1.46; optical film thickness,127 nm, were vapor deposited in the above order.

COMPARATIVE EXAMPLE 3

The present Comparative Example was carried out similarly to Example 3except for that the composition of the hard coating was modified.

As to the hard coating composition, 182 portions ofγ-glycidoxypropyltrimethoxysilane, 60 portions of tetraethoxysilane, 150portions of methyl alcohol was added, 47 portions of 0.01N hydrochloricacid were dropped while agitating, and further agitating for a night anda day, and the hydrolysate was prepared.

610 portions of the titanium oxide based complex particle “Optolake 1130F II”, as a catalyst, 20 portions of itaconic acid, 6 portions ofdicyanamide and 0.3 portion of the leveling agent “SILWET L-7001” wasadded to the relevant hydrolysate, agitated for a night and a day, andthe hard coating composition was prepared.

COMPARATIVE EXAMPLE 4

The present Comparative Example was carried out similarly to Example 4except for that the reflection prevention film was modified.

As to the reflection prevention film,

the lens was set in the lens dome for rotating the lens to which thehard coat film is provided, while the vacuum chamber was heated at 60°C., exhausted up to the pressure 1.33×10⁻³ Pa (1×10⁻⁵ torr), and afteroxygen ion cleaning was performed, from the substrate side,

The first layer, SiO₂: refractive index, 1.46; optical film thickness,26 nm;

The second layer, TiO₂; refractive index, 2.37; optical film thickness,33 nm;

The third layer, SiO₂; refractive index, 1.46; optical film thickness,47 nm;

The fourth layer, TiO₂; refractive index, 2.37; optical film thickness,265 nm; and,

The fifth layer, SiO₂; refractive index, 1.46; optical film thickness,125 nm, were in turn vapor deposited. Moreover, the oxygen ion assistvapor deposition was performed to Ti O₂of the second layer and thefourth layer. The obtained spectral reflection factor property is shownin FIG. 2.

EXAMPLE 5

(1) Preparation of Plastic Lens

3 portions of diisopropylperoxycarbonate which is the polymerizationinitiation agent was mixed with 100 portions of diethyleneglycol bis(arylcarbonate), filtered with 0.8 μmembrane filter, and the filtratewas injected into the glass-made template. Next, the filtrate was heatedat 40° C. for 3 hours, raised from 40° C. to 65° C. for 12 hours, from65° C. to 85° C. for 6 hours, and after finally heated at 85° C. for 3hours, the lens was taken out from the template, and further theannealing (distortion removal) was carried out at 130° C. for 2 hours,and the plastic lens having the refractive index of 1.5 was obtained.

(2) Primer processing

105 portions of colloidal silica “Oscar 1122G”, as a dilution solvent350 portions of methylalcohol, as a leveling agent one portion of“SILWET L-77” were mixed with 100 portions of TPEE “Pesresin A-160P”commercially available, agitated until it became in a uniformed state,then this was made as a primer paint.

Next, the plastic lens obtained in the foregoing (1) was immersed insodium hydroxide aqueous solution (concentration 10%) at the temperatureof 40° C., was washed with pure water, after the draining was performed,immersed in the composition of the foregoing primer paint. The lens wasdrawn up at the rate of 160 mm/min., the hardening was carried out underthe conditions of being at 110° C. for 20 minutes.

(3) Hard Coat Processing

97 portions of methyl alcohol was added to 109 portions ofγ-glycidoxypropyltrimethoxysilane, 40 portions of tetraethoxysilane, 27portions of γ-glycidoxypropylmethyldimethoxysilane, and 38 portions of0.01 N hydrochloric acid were dropped while agitating, and further,agitating for a night and a day and the hydrolysate was prepared.

390 portions of the colloidal silica “Methanol silica sol”, 290 portionsof pure water were added, and as a catalyst, 1.5 portions of ironacetylacetone and 3.0 portions of the leveling agent “SILWET L-77” wereadded to the relevant hydrolysate, agitating for a night and a day, andthe hard coating composition was prepared.

Next, after the primer processed lens processed in the foregoing (2) wasimmersed in the foregoing hard coating composition, the lens was drawnup at the rate of 105 mm/min., then, after undergoing pre-hardening at95° C. for 20 minutes, the hardening was performed at 100° C. for 2hours, and the hard coat film was formed.

(4) Reflection Prevention Processing

The lens was set in the lens dome for rotating the lens to which thehard coat film is provided, while the vacuum chamber was heated at 60°C., exhausted up to the pressure 1.33×10⁻³ Pa (1×10⁻⁵ torr), and afteroxygen ion cleaning was performed, from the substrate side,

The first layer, SiO₂; refractive index, 1.46; optical film thickness,26 nm;

The second layer, ZrO₂; refractive index, 2.05; optical film thickness,70 nm;

The third layer, SiO₂; refractive index, 1.46; optical film thickness,27 nm;

The fourth layer, ZrO₂; refractive index, 2.05; optical film thickness,135 nm; and,

The fifth layer, SiO₂; refractive index, 1.46; optical film thickness,135 nm, were in turn vapor deposited.

EXAMPLE 6

(1) Plastic Lens

A thiourethane based plastic lens having the refractive index of 1.60.

(2) Primer Processing

The present Example was carried out similarly to Example 5, except forthat 105 portions of colloidal silica was changed to 57 portions of thetitanium oxide based complex particle “Optolake 1120Z (S-7, G)”, and theamount of addition of portions of methyl alcohol was changed to 646portions.

(3) Hard Coat Processing

90 portions of methyl alcohol was added to 182 portions ofγ-glycidoxypropyltrimethoxysilane, 65 portions of tetraethoxysilane, and52 portions of 0.01 N hydrochloric acid were dropped while agitating,and further, agitating for a night and a day, and the hydrolysate wasprepared.

250 portions of the titanium oxide complex particle “Optolake 1130 FII”, 70 portions of pure water were added, and as a catalyst, 1.5portions of iron acetylacetone and 3.0 portions of the leveling agent“SILWET L-77” were added to the relevant hydrolysate, agitating for anight and a day, and the hard coating composition was prepared.

Next, after the primer processed lens processed in the foregoing (2) wasimmersed in the foregoing hard coating composition, the lens was drawnup at the rate of 105 mm/min., then, after undergoing pre-hardening at95° C. for 20 minutes, the hardening was performed at 100° C. for2hours, and the hard coat film was formed.

(4) Reflection Prevention Processing

The lens was set in the lens dome for rotating the lens to which thehard coat film is provided, while the vacuum chamber was heated at 60°C., exhausted up to the pressure 1.33×10⁻³ Pa (1×10⁻⁵ torr), and afteroxygen ion cleaning was performed, from the substrate side, The firstlayer, SiO₂: refractive index, 1.46; optical film thickness, 26 nm;

The second layer, ZrO₂; refractive index, 2.05; optical film thickness,83 nm;

The third layer, SiO₂; refractive index, 1.46; optical film thickness,21 nm;

The fourth layer, ZrO₂; refractive index, 2.05; optical film thickness,135 nm; and,

The fifth layer, SiO₂; refractive index, 1.46; optical film thickness,135 nm, were in turn vapor deposited.

EXAMPLE 7

The present Example was carried out similarly to Example 1 except forthat the primer processing was provided.

(1) Primer Processing

The processing was carried out similarly to Example 6 except for thatthe titanium oxide based complex particle was changed. The titaniumoxide based complex particle was changed to 85 portions of “Optolake1130Z (1)”.

EXAMPLE 8

The present Example was carried out similarly to Example 3 except forthat the primer processing was provided.

(1) Primer Processing

The processing was carried out similarly to Example 7 except for thatthe amount of addition of the titanium oxide based complex particle waschanged to 180 portions, methyl alcohol which is the diluent was changedto 350 portions.

COMPARATIVE EXAMPLE 5

The present Example was carried out similarly to Example 5 except forthat the primer paint was modified.

105 portions of colloidal silica “Oscar 1122G”, as a diluent 350portions of methylalcohol, as a leveling agent, one portion of “SILWETL-77” were mixed with 100 portions of aqueous emulsion polyurethane“Super Flex 150” commercially available, agitated until it became in auniformed state, then this was made as a primer paint.

COMPARATIVE EXAMPLE 6

The present Example was carried out similarly to Example 6 except forthat the primer paint was modified.

The primer paint was prepared similarly to Comparative Example 5 exceptfor that 105 portions of colloidal silica was changed to 82.5 portionsof the titanium oxide based complex particle “Optolake 1120Z (S-7, G)”,and the amount of addition of methylalcohol, which is the diluent, waschanged to 640 portions.

COMPARATIVE EXAMPLE 7

The present Example was carried out similarly to Example 7 except forthat the primer paint was modified.

The primer paint was prepared similarly to Comparative Example 6 exceptfor that the titanium oxide based complex particle was modified. Thetitanium oxide based complex particle was changed to 125 portions of“Optolake 1130Z (1)”.

COMPARATIVE EXAMPLE 8

The present Example was carried out similarly to Example 8 except forthat the primer paint was modified.

The primer paint was prepared similarly to Comparative Example 7 exceptfor that the amount of addition of the titanium oxide based complexparticle was changed to 203 portions, the amount of addition of methylalcohol was changed to 350 portions.

EXAMPLE 9

(1) Plastic Lens

The plastic lens manufactured similarly to Example 5.

(2) Preparation of Composition of Dye

After 3.2 portions of acrylic resin “Dianar BR-80” commerciallyavailable was resolved in 12.8 portions of toluene, 12 portions ofmethylethylketones, 12 portions of dioxane, as a leveling agent, 0.01portion of “SILWET L-7001” were mixed, agitated until it became in auniform state and the composition was prepared.

6 portions of the blue disperse dye “Sumikaron Blue-E-RPD”, 4 portionsof the red disperse dye “Sumikaron Red-E-RPD”, 2 portions of the yellowdisperse dye “Sumikaron Yellow-E-RPD” were added to the relevantcomposition, after agitating for 60 min., the filtration was carried outwith 3 μfilter, and the composition for dye was prepared.

(3) Preparation of Paint for Protective Film

Next, 85 portions of pure water was added to 15 portions of polyvinylalcohol (degree of polymerization, about 2,000), agitated until itbecame in a uniform state, and the paint for protective film wasprepared.

(4) Preparation of Dyed Lens

Next, the lens was wiped up with a cloth immersed in ethyl alcohol, theforegoing composition for dyeing was coated on the convex surface of therelevant lens by the spin coat method (Step 1:300 rpm×15 sec., Step2:1,000 rpm×15 sec.), after air drying, under the same conditions, thepaint for protective film was coated.

After this lens was heated at 130° C. for 30 minutes in an air-oven,immersed in water for 1 minute, then, immersed in acetone for 1 minute,and the dyed lens was obtained.

(5) Hard Coat Processing

Furthermore, this lens was immersed in sodium hydroxide aqueous solution(concentration 10) at the temperature of 40° C., was washed with purewater, after the draining was performed, was immersed in the hard coatcomposition used in Example 5. The lens was drawn up at the rate of 105mm/min., then, after pre-hardening at 95° C. for 20 minutes wasobtained, the hardening was performed at 110° C. for 2 hours, and thedyed lens hard coat processed product was obtained.

EXAMPLE 10

(1) Preparation of Plastic Lens

The thiourethane based plastic lens which is the same with that ofExample 1 (commercially available product)

(2) Preparation of Composition for Dyeing

The composition for dyeing was prepared similarly to Example 9.

(3) Preparation of Paint for Protective Film

The paint for protective film was prepared similarly to Example 9.

(4) Preparation of Dyed Lens

The dyed lens was manufactured similarly to Example 9.

(5) Hard Coat Processing The hard coat processing was carried outsimilarly to the hard coat processing in Example 1.

EXAMPLE 11

(1) Preparation of Plastic Lens

The plastic lens which is the same with that of Example 3.

(2) Preparation of Composition for Dyeing

The composition for dyeing was prepared similarly to Example 9.

(3) Preparation of Paint for Protective Film

The paint for protective film was prepared similarly to Example 9.

(4) Preparation of Dyed Lens

The dyed lens was manufactured similarly to Example 9 except for thatthe heating processing conditions in the air-oven was changed. Theheating processing conditions in the air-oven was changed to theconditions of 130° C.×60 min.

(5) Hard Coat Processing

The hard coat processing was carried out similarly to the hard coatprocessing in Example 3.

EXAMPLE 12

(1) Preparation of Plastic Lens

The plastic lens manufactured similarly to Example 5.

(2) Hard Coat Processing

Next, this lens was immersed in sodium hydroxide aqueous solution(concentration 10%) at the temperature of 40° C., was washed with purewater, after the draining was performed, was immersed in the compositionof the hard coat composition used in Example 5. The lens was drawn up atthe rate of 105 mm/min., then, after undergoing the pre-hardening at 95°C. for 20 minutes, the hardening was performed at ₁₀₀° C. for 2 hours,and the hard coat processing was carried out.

(3) Preparation of Composition for Dyeing

The composition for dyeing was prepared similarly to Example 9.

(4) Preparation of Paint for Protective Film

The paint for protective film was prepared similarly to Example 9.

(5) Dying of Hard Coat Processing Lens Next, the lens was wiped up witha cloth immersed in ethyl alcohol, the foregoing composition for dyeingwas coated on the convex surface of the relevant lens by the spin coatmethod (Step 1: 300 rpm×15 sec., Step 2: 1,000 rpm×15 sec.), after airdrying, under the same conditions, the paint for protective film wascoated.

After this lens was heated at 130° C. for 30 minutes in an air-oven,immersed in water for 1 minute, then, immersed in acetone for 1 minute,and the dyed lens was obtained.

EXAMPLE 13

(1) Preparation of Plastic Lens The plastic lens which is the same withthat of Example 5.

(2) Preparation of Composition of Dye

After 3.84 portions of acrylic resin “Dianar BR-80” commerciallyavailable was resolved in 15.36 portions of toluene, 14.4 portions ofmethylethylketones, 14.39 portions of dioxane, as a leveling agent, 0.01portion of “SILWET L-7001” were mixed, agitated until it became in auniform state and the composition was prepared.

2 portions of the ultraviolet ray absorbent “Ubinar D-50”. (the otherwater insoluble dye is not contained) was added to the relevantcomposition, after agitating for 60 min., the filtration was carried outwith 3 filter, and the composition for dye was prepared.

(3) Preparation of Paint for Protective Film

The paint for protective film was prepared similarly to Example 9.

(4) Preparation of Dyed Lens

The dyed lens was manufactured similarly to Example 9.

(5) Hard Coat Processing

The hard coat processing was carried out similarly to the hard coatprocessing in Example 9.

EXAMPLE 14

(1) Preparation of Plastic Lens

The plastic lens which is the same with that of Example 1.

(2) Preparation of Composition for Dyeing

The composition for dyeing was prepared similarly to Example 9.

(3) Preparation of Paint for Protective Film

The paint for protective film was prepared similarly to Example 9.

(4) Preparation of Concentration Gradation (half) Dyed Lens

Next, the lens was wiped up with a cloth immersed in ethyl alcohol, theforegoing composition for dyeing was coated on the convex surface of therelevant lens by the spin coat method (Step 1: 300 rpm×15 sec., Step 2:1,000 rpm×15 sec.), and after air drying, under the same conditions, thepaint for protective film was coated.

This lens was fixed, the hot air was blown on the convex surface of thelens by the heating gun from about 10cm upward of the surface. At thistime, the heating gun was shifted downward while the heating gun wasvibrated up and down, and further, the air at room temperature (23° C.)was hit to the portions on which the hot air have not been hit. Thisoperation was repeated for 3 minutes. (surface maximum temperature, 180°C.).

Next, this lens was immersed in water for 1 minute, then, immersed inacetone for 1 minute, and the dyed lens with concentration gradation wasobtained. For this concentration gradation lens, the portion which hasbeen located below at the time when the lens was fixed was colored asthe thickest portion and as going upward, the coloring became thinner.

(5) Hard Coat Processing

The hard coat processing was carried out similarly to the hard coatprocessing in Example 1.

EXAMPLE 15

(1) Preparation of Plastic Lens

The plastic lens which is the same with that of Example 3.

(2) Preparation of Composition for Dyeing

The composition for dyeing was prepared similarly to Example 9.

(3) Preparation of Paint for Protective Film

The paint for protective film was prepared similarly to Example 9.

(4) Preparation of Concentration Gradation (half) Dyed Lens

The preparation was carried out similarly to Example 14 except for thatthe heating time was changed to 5minutes.

(5) Hard Coat Processing

The hard coat processing was carried out similarly to the hard coatprocessing in Example 3.

COMPARATIVE EXAMPLE 9

(1) Preparation of Plastic Lens

The plastic lens which is the same with that of Example 5.

(2) Preparation of Composition for Dyeing

2 portions of “Sumikaron Blue-E-RPD”, 1 portion of “SumikaronRed-E-RPD”, 1 portion of “Sumikaron Yellow-E-RPD”, and as a surfactant,3 portions of “Rhevenol V-700” were added to 1,000 portions of water,and after agitating, heated up to 90° C. and the composition for dyeingwas prepared.

(3) Preparation of Dyed Lens

Next, the lens was wiped up with a cloth immersed in ethyl alcohol,immersed in the foregoing composition for dyeing for 30 minutes, and thedyed lens was obtained.

(4) Hard Coat Processing

The hard coat processing was carried out similarly to the hard coatprocessing in Example 9.

COMPARATIVE EXAMPLE 10

(1) Preparation of Plastic Lens

The plastic lens was prepared similarly to Example 1.

(2) Preparation of Composition for Dyeing

The composition for dyeing was prepared similarly to Comparative Example9.

(3) Preparation of Dyed Lens

The preparation of dyed lens was carried out similarly to ComparativeExample 3.

(4) Hard Coat Processing

The hard coat processing was carried out similarly to the hard coatprocessing in Example 1.

COMPARATIVE EXAMPLE 11

(1) Preparation of Plastic Lens

The plastic lens was prepared similarly to Example 3.

(2) Preparation of Composition for Dyeing

The composition for dyeing was prepared similarly to Comparative Example9.

(3) Preparation of Dyed Lens

The preparation of dyed lens was carried out similarly to ComparativeExample 9 except for that the immersion time in the composition fordyeing was changed. The immersion time was changed to 120 minutes.

(4) Hard Coat Processing

The hard coat processing was carried out similarly to the hard coatprocessing in Example 3.

COMPARATIVE EXAMPLE 12

(1) Preparation of Plastic Lens

The plastic lens was prepared similarly to Example 5.

(2) Hard Coat Processing

The hard coat processing was carried out similarly to Example 12.

(3) Preparation of Composition for Dyeing

The composition for dyeing was prepared similarly to Comparative Example9.

(4) Preparation of Dyed Lens

Next, the hard coat processed lens was wiped up with a cloth immersed inethyl alcohol, then, immersed in the foregoing composition for dyeingfor 30 minutes, and the dyed lens was obtained.

COMPARATIVE EXAMPLE 13

(1) Preparation of Plastic Lens

The plastic lens was prepared similarly to Example 5.

(2) Preparation of Composition for Dyeing

2 portions of the ultraviolet ray absorbent “Ubinar D-50” and as asurfactant, 3 portions of “Rhevenol V-700” were added to 1,000 portionsof water, and after agitating, heated up to 90° C. and the compositionfor dyeing was prepared.

(3) Preparation of Dyed Lens

The preparation of dyed lens was carried out similarly to ComparativeExample 10.

(4) Hard Coat Processing

The hard coat processing was carried out similarly to the hard coatprocessing in Example 9.

COMPARATIVE EXAMPLE 14

(1) Preparation of Plastic Lens

The plastic lens which is the same plastic lens with that of Example 1.

(2) Preparation of Composition for Dyeing

The composition for dyeing was prepared similarly to Comparative Example9.

(3) Preparation of Dyed Lens

Next, the lens was wiped up with a cloth immersed in ethyl alcohol,then, immersed in the foregoing composition for dyeing for 10 minutesusing the half dyeing apparatus (Nikon half dyeing apparatus, made byNikon Corporation), and the dyed lens was obtained.

(4) Hard Coat Processing

The hard coat processing was carried out similarly to the hard coatprocessing in Example 1.

COMPARATIVE EXAMPLE 15

(1) Preparation of Plastic Lens

The plastic lens which is the same plastic lens with that of Example 3.

(2) Preparation of Composition for Dyeing

The composition for dyeing was prepared similarly to Comparative Example9.

(3) Preparation of Dyed Lens

The preparation of dyed lens was carried out similarly to ComparativeExample 14 except for that the immersion time in the composition fordyeing was changed. The immersion time was changed to 60 minutes.

<Evaluation Items>

(1) Interference Fringes

The light of fluorescent lamp “trade name: Mellow 5N” (made by ToshibaLighting & Technology Corporation, three band neutral white fluorescentlamp) was reflected on the surface of test piece, and determined by thedegree of its optical interference color (rainbow pattern) formed on thesurface of the object.

(2) Adhesiveness

100 pieces of squares were formed on the test piece at 1 mm intervals in1 cm square, after the cellophane-made adhesive tape was stronglypressed on it, rapidly peeled off in the 90 degrees direction, repeated10 times, and the number of squares which have not peeled off wascounted.

(3) Scraping and Damaging Resistance

The load of (0.6 kgf) was added on the steel-wool (#0000), the surfaceof each test piece was scraped 30 times/15 sec., and determineddepending on the degree of damage.

3A: the area of damage was 0%,

2A: the area of damage exceeded over 1%, less than 2%,

A: the area of damage exceeded over 3%, less than 10%,

AB; the area of damage exceeded over 10%, less than 30%,

B: the area of damage exceeded over 30%, less than 60%,

C: the area of damage was more than 60%, and

D: the area of damage was the whole area.

(4) Hot Water Resistance

The test piece was immersed in a hot water at 80° C. for 10 minutes, itsappearance (the presence or absence of crack) and adhesiveness test(described above) were carried out.

(5) Heat Resistance

Each test piece was heated for 5 minutes using “Perfect Oven” (tradename: made by Tabai Espec, Corp.), and after leaving at room temperaturefor 30 minutes, determined with the presence or absence of crack.

The temperature started from 60° C., raised the temperature at intervalsof 10° C., the highest temperature that the crack was not recognized wasmade the heat resistance temperature.

(6) Weatherability

Exposed to the accelerated weathering test (“Sunshine Super Long LifeWeather Strip meter”, made by Suga Test Instruments) for 200 hours, theappearance (surface state) and adhesiveness test (described above) wascarried out.

(7) Measurements of Reflection Prevention Area and Spectral LuminousEfficacy

Using reflectometry (“USP-II”, made by Olympus Optical, Co., Ltd.), themeasurements were carried out.

(8) Measurement of Spectral Luminous Transmittance

Using the spectral luminous transmissonmeter (“STS-2”, made by FujiKoden, Co., Ltd.), measurement was carried out.

(9) Measurement of Spectral Luminous Transmittance After Ultraviolet RayIrradiation

The measurement of spectral luminous transmittance (described above) wascarried out after the mercury lamp for discoloration test (“H400-F”,Toshiba Lighting & Technology, Corp.) was emitted and the test piece wasexposed to the lamp at the distance of about 20 cm for 50 hours.

(10) Shock Resistance

Steel ball (33 g) was dropped from the height of 127 cm on the centerportion of the test piece, determined depending on whether it wascracked or not.

(11) 400 nm Transmittance

Using spectrophotometer (“UV-1200”, made by Shimazu, Corp.),transmittance of 400 nm was measured.

TABLE 1 Reflection Lens Hard film prevention film Example 1 1.67 Metalparticle(1) Ion cleaning: done Hardening agent: Assist deposition: donealuminum Equivalent film acetylacetone configuration: medium, highrefractive index Example 2 1.67 Metal particle(1) Same as Example 1Hardening agent: iron acetylacetone Example 3 1.74 Metal particle(2) Ioncleaning: done Hardening agent: Assist deposition: done aluminumEquivalent film acetylacetone configuration: medium, high refractiveindex Example 4 1.74 Metal particle(2) Ion cleaning: done Hardeningagent: Assist deposition: done iron acetylacetone Equivalent filmconfiguration: medium, high refractive index Comparative 1.67 Metalparticle(3) Same as Example 1 Example 1 Hardening agent: itaconic acidand dicyandiamide Comparative 1.67 Same as Example 2 Ion cleaning: doneExample 2 Assist deposition: none Equivalent film configuration: mediumrefractive index Comparative 1.74 Metal particle(3) Same as Example 3Example 3 Hardening agent: itaconic acid and dicyandiamide Comparative1.74 Same as Example 4 Ion cleaning: done Example 4 Assist deposition:none Equivalent film configuration: medium refractive index Metalparticle (1) “Optolake 1130Z (1)” Metal particle (2) “Optolake 1130Z(2)” Metal particle (3) “Optolake 1130F II”

TABLE 2 Reflection Lens Primer Hard film prevention film Example 5 1.50Polyester Colloidal Ion cleaning: based TPE silica done Hardening Assistdeposit: agent: iron none acetylacetone Equivalent film configuration:High refractive index Example 6 1.60 Polyester Metal Ion cleaning: basedTPE particle(3) done Hardening Assist deposit: agent: iron noneacetylacetone Equivalent film configuration: High refractive indexExample 7 1.67 Polyester Same as Example 1 based TPE Example 8 1.74Polyester Same as Example 3 based TPE Comparative 1.50 Poly-urethaneSame as Example 5 Example 5 Based TPU Comparative 1.60 Poly-urethaneSame as Example 6 Example 6 Based TPU Comparative 1.67 Poly-urethaneSame as Example 7 Example 7 Based TPU (Same as Example 1) Comparative1.74 Poly-urethane Same as Example 8 Example 8 Based TPU (Same asExample 3) Metal particle (3): “Optolake 1130 F II”

TABLE 3 Lens Dyeing Hard film Example 9 1.50 Sublimation type dyeingSame as Example 5 Example 10 1.67 Sublimation type dyeing Same asExample 1 Example 11 1.74 Sublimation type dyeing Same as Example 3Example 12 1.50 Sublimation type dyeing Same as Example 5 Coloring afterhard film formation Example 13 1.50 Sublimation type dyeing Same asExample 5 Ultraviolet ray absorbent Example 14 1.67 Sublimation typedyeing Same as Example 1 With concentration gradation Example 15 1.74Sublimation type dyeing Same as Example 3 With concentration gradationComparative 1.50 Dip dyeing method Same as Example 9 Example 9Comparative 1.67 Dip dyeing method Same as Example 10 Example 10Comparative 1.74 Dip dyeing method Same as Example 11 Example 11Comparative 1.50 Dip dyeing method Same as Example 12 Example 12Coloring after hard film formation Comparative 1.50 Dip dyeing methodSame as Example 13 Example 13 Ultraviolet ray absorbent Comparative 1.67Dip dyeing method Same as Example 14 Example 14 With concentrationgradation Comparative 1.74 Dip dyeing method Same as Example 15 Example15 With concentration gradation

TABLE 4 Test piece No. 1 2 3 4 5 6 T st piece Example 5 Example 6Example 7 Example 8 Comparative Comparative Example 5 Example 6Interference excellent excellent excellent excellent excellent excellentfringes Adhesiveness 100/100 100/100 100/100 100/100 100/100 100/100Scraping and A AB A A A AB damaging resistance Hot water excellentexcellent excellent excellent excellent excellent resistance, appearanceHot water 100/100 100/100 100/100 100/100 100/100 100/100 resistance,adhesiveness H at resistance 70° C. 90° C. 90° C. 100° C. 60° C. 80° C.Shock resistance Not cracked Not cracked Not Cracked Not Cracked NotCracked Not Cracked Test piece No. 7 8 9 10 11 12 Test piece ComparativeComparative Example 5: Example 6: Example 7: Example 8: Example 7Example 8 Primer film Primer film Primer film Primer film none none nonenone (Example 1) (Example 3) Interference excellent excellent excellentexcellent excellent excellent fringes Adhesiveness 100/100 100/100100/100 100/100 100/100 100/100 Scraping and A A A AB A A damagingresistance Hot water excellent excellent excellent excellent excellentexcellent resistance, appearance Hot water 100/100 100/100 100/100100/100 100/100 100/100 resistance, adhesiveness Heat resistance 80° C.90° C. 70° C. 90° C. 90° C. 100° C. Shock resistance Not cracked Notcracked Cracked Cracked Cracked Cracked

Comparative Example 1 is inferior at scraping and damaging resistance inthe hard coat, and the lowering of spectral luminous transmittance ofthe reflection prevention processed product due to ultraviolet rayirradiation is significant. It is considered that this is caused by thetitanium oxide complex particle contained in the hard coat.

Comparative Example 2 is low at scraping and damaging resistance andheat resistance of the reflection prevention processed product. This isdue to the difference of the film-forming conditions of the reflectionprevention film.

For comparative Example 3, interference fringes are slightly recognized,and the spectral luminous transmittance due to ultraviolet rayirradiation of the reflection prevention processed product issignificant similar to Comparative Example 1.

Comparative Example 4 is excellent at durability, however, thereflection prevention band in the visible light area was narrowercomparing with Example (see FIG. 1 and FIG. 2).

Examples 1-4 were excellent in all the items.

TABLE 5 Comparative Comparative Comparative Comparative Example 1Example 2 Example 3 Example 4 Example 1 Example 2 Example 3 Example 4 HDInterference Excellent Excellent Excellent Excellent Excellent ExcellentSome Excellent Fringes Adhesiveness 100/100 100/100 100/100 100/100100/100 100/100 100/100 100/100 Scraping and damaging A - AB A - AB A -AB A - AB AB A - AB A - AB A - AB resistance Hot water resistance:Excellent Excellent Excellent Excellent Excellent Excellent ExcellentExcellent appearance Hot water resistance: 100/100 100/100 100/100100/100 100/100 100/100 100/100 100/100 adhesiveness HD + ARInterference Excellent Excellent Excellent Excellent Excellent ExcellentSome Excellent Fringes Adhesiveness 100/100 100/100 100/100 100/100100/100 100/100 100/100 100/100 Scraping and damaging A A A A AB AB A Aresistance Hot water resistance: Excellent Excellent Excellent ExcellentExcellent Excellent Excellent Excellent appearance Hot water resistance:100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100adhesiveness Heat resistance 90° C. 90° C. 100° C. 100° C. 90° C. 80° C.100° C. 100° C. Weatherability: Excellent Excellent Excellent ExcellentExcellent Excellent Excellent Excellent Appearance Weatherability:100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100Adhesiveness Reflection prevention Wide area Wide area Wide area Widearea Wide area Wide area Wide area Rather area Wide area Spectralluminous 0.35% 0.35% 0.34% 0.35% 0.35% 0.32% 0.32% 0.35% reflectanceSpectral luminous 99.0% 99.0% 98.7% 98.6% 99.0% 99.1% 98.6% 98.6%transmittance Spectral luminous 97.8% 97.8% 97.3% 97.6% 94.8% 97.9%93.3% 97.4% transmittance after ultraviolet ray irradiation

The test pieces Nos. 1-4 using the TPEE based primer of Examples 5-8have heat resistance comparable to the primer non-coated test piecesNos. 9-12 as well as are excellent at appearance similar to the testpieces Nos. 5-8 using the TPU based primer of Comparative Examples 5-8corresponding to these, and at adhesiveness, scraping and damagingresistance, hot water resistance and shock resistance. Specifically, thetest pieces Nos. 1-4 are excellent at heat resistance comparing with thetest pieces Nos. 5-8 using the TPU based primer of Comparative Examples5-8.

TABLE 6 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14Example 15 Dyeing processing time 30 min. 30 min. 60 min. 30 min. 30min. 3 min. 5 min. Coloring concentration Spectral luminous 8.5% 15.2%58.2% 23.1% — 6.1% 28.3% transmittance 400 nm — — — — 15.8% — —transmittance Spectral luminous 9.7% 15.9% 58.7% — 16.2% 6.4% 28.6%transmittance after HD Comparative Comparative Comparative ComparativeComparative Comparative Comparative Example 9 Example 10 Example 11Example 12 Example 13 Example 14 Example 15 Dyeing processing time 30min. 30 min. 120 min. 30 min. 30 min. 10 min. 60 min. Coloringconcentration Spectral luminous 23.8% 20.1% 83.1% 45.8% — 49.4% 79.7%transmittance 400 nm — — — — 52.3% — — transmittance Spectral luminous28.1% 26.4% 83.8% — 54.1% 56.8% 80.9% transmittance after HD

Examples 9-15 by sublimation tendency dyeing can be colored in a shorttime up to a high concentration and the fastness after the processing(HD) are also excellent comparing with the corresponding ComparativeExamples 9-15 by the conventional dyeing.

What is claimed is:
 1. An optical element comprising a primer layerbetween an organic glass base material and a silicone based hardeningcoating film, said primer layer comprising: a primer layer formationpolymer; wherein the primer layer formation polymer is a polyester basedthermoplastic elastomer, also known as ester based TPE.
 2. A primercomposition that forms all or part of a primer layer between an organicglass base material and a silicone based hardening coating filmcomprising: a primer layer formation polymer; wherein the primer layerformation polymer is an ester based TPE, and the primer layer furthercomprises a metal oxide particle; wherein the metal oxide particle is anoptical interference control agent.
 3. The primer composition as claimedin claim 2, characterized in that weight ratio of hard segment and softsegment of said ester based TPE is the former/the latter=30/70-90/10,and said ester based TPE indicates surface hardness (Shore hardness D):35-75, bend elasticity: 40-800 MPa.
 4. The primer composition as claimedin claim 1, characterized in that weight ratio of hard segment and softsegment of said ester based TPE is the former/the latter=30/70-90 /10,and said ester based TPE indicates surface hardness (Shore hardness D):35-75, bend elasticity: 40-800 MPa.
 5. The silicone based hardeningcoating film of claim 1, wherein a hard coat composition that forms saidsilicone based hardening coating film is a hard coat compositionconsisting of hydrolysate of alkoxysilane whose main body istrialkoxysilane containing a monoepoxy organic group as a matrixformation ingredient, and titanium based metal oxide complex particle asan optical interference control agent, and said titanium based metaloxide complex particle is consists of TiO₂ as a main ingredient, andSiO₂ as a major sub-ingredient, and further, ZrO₂ and K₂O as a tracesub-ingredient.
 6. The silicon based hardening coating film of claim 5,wherein for said titanium based metal oxide complex particle, averagediameter thereof is made as one being in a range of 1-50 nm, compositionthereof is made as one satisfying each weight ratio ofSiO₂/TiO₂=0.1900-0.2100, ZrO₂/TiO₂=0.0015-0.023, K₂O/TiO₂=0.0012-0.012,content thereof is in a range of 40-100 weight portions to 100 weightportions of whole alkoxysilane content.
 7. The silicon based hardeningcoating film of claim 6, wherein said trialkoxysilane containing saidmonoepoxy organic group consists of one or more than species selectedfrom the group represented by general formula (1):

(where R¹ represents H or CH₃, R² represents alkylene group having 1-4of carbon atoms and R³ represents alkyl group having 1-4 of carbonatoms), or represented by general formula (2):

(where R¹ represents alkylene group having 1-4 of carbon atoms and R²represents alkyl group having 1-4 of carbon atoms).
 8. The silicon basedhardening coating film of claim 7, wherein the hardening compositionfurther contains in addition to said trialkoxysilane containing saidmonoexpoxy organic group a tetraalkoxysilane represented by generalformula (3): Si (OR¹)₄ (where R¹ represents alkyl group having 1-4 ofcarbon atoms), the content of the tetraalkoxysilane being 20 wt % orless of the total content of said alkoxysilane.
 9. The silicon basedhardening coating film of claim 8, wherein said hard coat compositioncontains an organic metal compound as a hardening agent of the matrixformation ingredient, the relevant organic metal compound consists ofone or more species selected from the group of chelate compounds of Cr(III), Co (III), Fe (III), Zn (II), In (III), Zr (IV), Y (III), Sn, V,Al (III), Ti (II) with which chelating agent selected fromethylenediamine-tetraacetic acid, hexafluoroacetylacetone,trifluoroacetylacetone, acetylacetone and methyl acetoacetatecoordinates.
 10. A method of forming an optical element comprising thesteps of: forming a hard coat layer on a surface of an organic glassbase material via a primer layer, wherein said primer layer comprises aprimer layer formation polymer wherein all or part of the primer layerformation polymer is an ester based TPE, wherein said hard coat layercomprises a hard coat composition, said hard coat composition comprisinghydrolysate of alkoxysilane whose main body is trialkoxysilanecontaining monoepoxy organic group as a matrix formation ingredient, andtitanium based metal oxide complex particle as an optical interferencecontrol agent, and wherein said titanium based metal oxide complexparticle comprises TiO₂ as a main ingredient, SiO₂ as a majorsub-ingredient and further ZrO₂ and K₂O as a trace sub-ingredient. 11.The method of forming an optical element as claimed in claim 10, whereinsaid primer composition further comprises a metal oxide particle as anoptical interference control agent.
 12. The method of forming an opticalelement as claimed in claim 10 or 11, wherein said organic glass basematerial is obtained by polymerizing and reacting (1) one or more activehydrogen compounds selected from the group consisting of polyols,polythiols and hydroxy compounds having a mercapto group, and (2) one ormore compounds selected from the group of polyisothiocyanate compoundsor isothiocyanate compounds having an isocyanate group, or a compoundobtained by polymerizing and reacting episulfide having cyclic skeletonhaving two or more equivalents of a structure represented by generalformula (4):

where X represents S or O and the amount of S is 50% or more on averagewith respect to total of S and O constituting the three membered ring.13. The method of forming an optical element as claimed in claim 10,further comprising the step of laminating a reflection prevention filmlayer on said hard coat layer.
 14. The method of forming an opticalelement as claimed in claim 13, wherein said reflection prevention filmwhose design center wavelength λ is made in a range of 450-550 nm, has amultilayer structure having a medium refractive index layer having anoptical film thickness of 0.19-0.29 λ, a high refractive index layerhaving an optical film thickness of 0.42-0.58 λ, and a low refractiveindex layer having an optical film thickness of 0.19-0.29 λ are in turnformed.
 15. The method of forming an optical element as claimed in claim14, wherein said medium refractive index layer and said high refractiveindex layer are comprised of an equivalent film comprising two or morelayers having different refractive index substances.
 16. A method offorming an optical element as claimed in claim 13, 14 or 15, furthercomprising the step of film-forming method of a reflection preventionfilm, wherein ion cleaning processing is performed on said hard coatlayer surface prior to the film-forming of a reflection prevention film.17. The method of forming an optical element as claimed in claim 16,wherein film-forming of at least high refractive index layer out of saidreflection prevention films is performed by vapor deposition using anion beam assist method.
 18. A method of forming optical elementcomprising the steps of: forming a hard coat layer on an organic glassbase material surface via a primer layer and sublimely dyeing an organicglass base material, wherein said primer layer comprises a primer layerformation polymer wherein all or part of the primer layer formationpolymer is an ester based TPE, wherein said hard coat layer comprises ahard coat composition, said hard coat composition comprising hydrolysateof alkoxysilane whose main ingredient is trialkoxysilane containingmonoepoxy organic group as a matrix formation ingredient, and titaniumbased metal oxide complex particle as an optical interference controlagent, wherein said titanium based metal oxide metal complex particlecomprises TiO₂ as a main ingredient, SiO₂ as a major sub-ingredient andfurther ZrO₂ and K₂O as a trace sub-ingredient, and wherein thecomposition used for said sublimation type dyeing step comprises a anacrylic resin sizing agent, a water insoluble dye, and an organicsolvent having 8-11 of a SP value (resolving property parameter) as adye resolving agent.
 19. The method of forming an optical element asclaimed in claim 18, wherein said primer composition further contains ametal oxide particle as an optical interference control agent.
 20. Themethod of forming an optical element as claimed in claim 18 or 19,wherein said organic glass base material is obtained by polymerizing andreacting (1) one or more active hydrogen compounds selected from thegroup of polyols, polythiols, and hydroxy compounds having a mercaptogroup, and (2) one or more compounds selected from the group ofpolyisothiocyanate compounds or isothiocyanate compounds having anisocyanate group, or a compound obtained by polymerizing and reactingepisulfide compounds having cyclic skeleton having two or more ofequivalents of a structure represented by general formula (4):

where X represents S or O and the amount of S is 50% or more on averagewith respect to total of S and O constituting the three membered ring.21. A method of using the primer composition of any of claim 1, 2, 3 or4, whereby the primer layer is placed between said organic glass basematerial and said silicone based hardening coating film to form anoptical element.